Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same

ABSTRACT

The present invention relates to a transition metal complex represented by the formula (I): 
     
       
         
         
             
             
         
       
     
     wherein M represents a Group 4 transition metal;
         —Y— represents   (a): —C(R 1 )(R 20 )-A-,   (b): —C(R 1 )(R 20 )-A 1 (R 30 )—,   (c): —C(R 1 )=A 1 -, or   (d): —C(R 1 )=A 1 -A 2 -R 30 ;   A represents a Group 16 element and A 1  and A 2  each represents a Group 15 element;   R 1  to R 9 , R 20 , and R 30  are the same or different and each represents an optionally substituted hydrocarbon group, etc.; and X 1  and X 2  are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C 1-10  alkyl group, etc., and an intermediate product thereof, and a catalyst for olefin polymerization which comprises said transition metal complex as a component.

TECHNICAL FIELD

The present invention relates to a transition metal complex and acatalyst for olefin polymerization comprising said complex, and to aprocess for production of olefin polymer using the same.

BACKGROUND ART

As a half-metallocene catalyst for olefin polymerization,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (JP-A 3-163088) anddimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido)titaniumdichloride (JP-A 9-87313) have been respectively disclosed. However,production processes of these transition metal complexes require use ofsilicon compounds as a key intermediate, which is sensitive to moistureand difficult to be handled. Therefore, a catalyst that can be handledmore easily and can afford various olefin polymers has been desired.

DISCLOSURE OF INVENTION

According to the present invention, a transition metal complex can beobtained using a ligand intermediate that can be produced and handledmore easily, without using a silicon compound that is sensitive tomoisture and difficult to be handled as a key intermediate, and acatalyst capable of producing various olefin polymers can be obtainedusing said transition metal complex as a catalyst component.

Namely, the present invention provides the following:

1. the formula (I):

wherein M represents a Group 4 transition metal;

—Y— represents

(a): —C(R¹)(R²⁰)-A-,

-   -   (b): —C(R¹)(R²⁰)-A¹(R³⁰)—,    -   (c): —C(R¹)=A¹-, or

(d):

wherein A¹ and A² coordinate to M;

A represents a Group 16 element, A¹ and A² each represent a Group 15element;

R¹ and R²⁰ are the same or different and each represents a hydrogenatom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₆₋₂₀ aryl group oran optionally substituted C₇₋₂₀ aralkyl group;

R³⁰ represents a hydrogen atom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₇₋₂₀ aralkyl group ora silyl group optionally substituted with optionally substituted C₁₋₂₀hydrocarbon(s);

R², R³, R⁴ and R⁵ are the same or different and each represents ahydrogen atom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), ora C₁₋₂₀ hydrocarbon-substituted amino group;

R⁶, R⁷, R⁸ and R⁹ are the same or different and each represents ahydrogen atom, a halogen atom, an optionally substituted C₁₋₁₀ alkylgroup,

an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₆₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), ora C₁₋₂₀ hydrocarbon-substituted amino group; and

X¹ and X² are the same or different and each represents a hydrogen atom,a halogen atom,

an optionally substituted Cl₁₋₁₀ alkyl group,an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group ora C₁₋₂₀ hydrocarbon-substituted amino group, or

X¹ and X², R¹ and R²⁰, the adjacent R², R³, R⁴ and R⁵ or the adjacentR⁶, R⁷, R⁸ and R⁹ may be linked to each other to form a ring;

provided that when —Y— represents (a), there is no case that both R¹ andR²⁰ represent hydrogen atoms and R², R³, R⁴ and R⁵ are taken togetherwith the cyclopentadiene ring to form a 2-methylinden-1-yl group;

2. a catalyst for olefin polymerization comprising the above-mentionedtransition metal complex in combination with the following compound (A):

wherein (A) represents at least one compound selected from the followingcompounds (A1) to (A3):

(A1): an organic aluminum compound represented by the formulaE1_(a)Al(Z)_((3-a)),

(A2): cyclic aluminoxane having the structure represented by the formula{—Al(E2)-O—}_(b), and (A3): linear aluminoxane having the structurerepresented by the formula E3{-Al(E3)-O—}_(c)Al(E3)₂,

wherein E1 to E3 are the same or different and each represents a C₁₋₈hydrocarbon group;

Z are the same or different and each represents a hydrogen atom or ahalogen atom; and

a is 1, 2 or 3, b is an integer of not less than 2, and c is an integerof not less than 1;

3. a catalyst for olefin polymerization comprising the above transitionmetal complex in combination with the compound (A) and further (B),

wherein (B) represents at least one compound selected from the followingcompounds (B1) to (B3):

(B1): a boron compound represented by the formula BQ₁Q₂Q₃,

(B2): a boron compound represented by the formula Z⁺(BQ₁Q₂Q₃Q₄)⁻, and

(B3): a boron compound represented by the formula (L-H)⁺(BQ₁Q₂Q₃Q₄)⁻,

wherein B is a boron atom in a trivalent valence state;

Q₁ to Q₄ are the same or different and each represents a halogen atom,

a C₁₋₂₀ hydrocarbon group,a C₁₋₂₀ halogenated hydrocarbon group,a silyl group substituted with C₁₋₂₀ hydrocarbon group(s),a C₁₋₂₀ alkoxy group, oran amino group substituted with two C₂₋₂₀ hydrocarbon groups;

L-H represents a Brønsted acid; and

Z are the same or different and each represents an inorganic or organiccation (for example, a hydrogen atom, a halogen atom or a tritylcation);

4. a process for producing an olefin polymer, comprising polymerizingolefin using the above-mentioned catalyst for olefin polymerization;5. a substituted cyclopentadiene ligand represented by the formula (II):

wherein —Y— represents

(a′): —C(R¹)(R²⁰)-A-H,

(b′): —C(R¹)(R²⁰)-A¹(R³⁰)—H,

(c′): —C(R¹)=A¹-H

(d′):

(e):—C(R¹)=A¹-R³⁰

(f): —CH=A¹-OR⁺, or

(g): —CN; and

R¹, R²R³, R⁴, R⁵, R⁶R⁷, R⁸, R⁹, R²⁰, R³⁰, A, A¹ and A² have the samemeanings as defined above;

provided that:

1) when —Y′ represents (a′), neither R² and R³ nor R⁴ and R⁵ are takentogether with the cyclopentadiene ring to form a fluorene ring or anindenyl ring; and

2) when —Y′ represents (g), neither R² and R³ nor R⁴ and R⁵ are takentogether with the cyclopentadiene ring to form a fluorene ring, and thecompound represented by the formula (II) is not2-(4-methoxyinden-1-yl)benzonitrile; furthermore, regarding the doublebonds of the cyclopentadiene ring, their positions are not limited tothe positions as depicted in the formula and are optional or thecyclopentadiene ring represents a mixture of isomers having the doublebonds in any positions, or an intermediate product thereof;

6. a process for producing a transition metal complex represented by theformula (I), which comprises reacting a substituted cyclopentadienerepresented by the formula (II), wherein —Y′ represents any of (a′) to(d′) with a transition metal compound represented by the formula (III):

MX¹X²X³X⁴  (III)

wherein M represents a Group 4 transition metal; and

X¹, X², X³ and X⁴ are the same or different and each represents ahydrogen atom, a halogen atom,

a C₁₋₁₀ alkyl group,a C₁₋₁₀ alkoxy group,a C₆₋₂₀ aryl group,a C₆₋₂₀ aryloxy group,a C₇₋₂₀ aralkyl group,a C₇₋₂₀ aralkyloxy group, ora C₁₋₂₀ hydrocarbon-substituted amino group;7. a carbonyl compound represented by the formula (I):

wherein R¹ represents a hydrogen atom,an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₆₋₂₀ aryl group, oran optionally substituted C₇₋₂₀ aralkyl group;

R², R³, R⁴ and R⁵ are the same or different and each independentlyrepresents a hydrogen atom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), ora C₁₋₂₀ hydrocarbon-substituted amino group; and

R⁶, R⁷, R⁸ and R⁹ are the same or different and each independentlyrepresents a hydrogen atom, a halogen atom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s) ora C₁₋₂₀ hydrocarbon-substituted amino group, orthe adjacent R², R³, R⁴ and R⁵ and the adjacent R⁶, R⁷, R⁸ and R⁹ linkwith each other to form a benzene ring or a cycloalkylene ring;

provided that

1) the positions of the double bonds in the cyclopentadiene ring areoptional or the cyclopentadiene ring represents a mixture of compoundshaving double bonds at optional positions; and

2) neither R² and R³ nor R⁴ and R⁵ are taken together with thecyclopentadiene ring to form a fluorene ring or an indenyl ring;

8. a process for producing a substituted cyclopentadiene compoundrepresented by the formula (I), which comprises reacting a halogencompound represented by the formula (2):

wherein R¹, R⁶, R⁷, R⁸ and R⁹ have the same meaning as defined below;

R¹⁰ and R¹¹ are the same or different and each represents an optionallysubstituted C₁₋₁₀ alkyl group, or they are linked to each other at theirends and taken together with oxygen atoms and a carbon atom to whichsaid oxygen atoms are attached to form a 5- or 6-membered ring; and

X represents a chlorine, bromine or iodine atom, with cyclopentenonerepresented by the formula (3):

wherein R², R³, R⁴ and R⁵ have the same meaning defined below, in thepresence of a magnesium compound or an organic lithium compound to givecyclopentenol represented by the formula (4):

wherein R¹ represents a hydrogen atom,an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₆₋₂₀ aryl group, oran optionally substituted C₇₋₂₀ aralkyl group;

R², R³⁴, R⁴ and R⁵ are the same or different and each represents ahydrogen atom,

an optionally substituted C₁₋₁₀ alkyl group,an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), ora C₁₋₂₀ hydrocarbon-substituted amino group;

R⁶, R⁷, R⁸ and R⁹ are the same or different and each independentlyrepresents a hydrogen atom, a halogen atom, an optionally substitutedC₁₋₁₀ alkyl group,

an optionally substituted C₁₋₁₀ alkoxy group,an optionally substituted C₆₋₂₀ aryl group,an optionally substituted C₆₋₂₀ aryloxy group,an optionally substituted C₇₋₂₀ aralkyl group,an optionally substituted C₇₋₂₀ aralkyloxy group,a silyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s) ora C₁₋₂₀ hydrocarbon-substituted amino group, or

the adjacent R², R³, R⁴ and R⁵ and the adjacent R⁶, R⁷, R⁸ and R⁹ arelinked to each other to form a benzene ring or a cycloalkylene ring; and

R¹⁰ and R¹¹ have the same meanings as defined above, and treating saidcompound with an acid; and

9. the cyclopentenol represented by the formula (4).

MODE FOR CARRYING OUT THE INVENTION

Hereinafter the substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²⁰ andR³⁰ for the compounds of the above-mentioned formulas (I), (II), and (1)to (4) and for the following compounds (5) to (13) are explained.

Specific examples of the optionally-substituted C₁₋₁₀ alkyl group forthe substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²⁰, R³⁰ and X¹ toX⁴ include a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, an-octyl group and a n-decyl group. Furthermore, the above substituentswhich are substituted with halogen atom(s) (especially fluorine atom(s))are exemplified, and specific examples thereof include a fluoromethylgroup, a difluoromethyl group, a trifluoromethyl group, a fluoroethylgroup, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethylgroup, a pentafluoroethyl group, a perfluoropropyl group, aperfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, aperfluorooctyl group, a perfluorodecyl group, a trichloromethyl group,and the like. Among these, a methyl group, an ethyl group, an isopropylgroup, a tert-butyl group, an amyl group and the like are preferred.

The optionally substituted C₆₋₂₀ aryl group for R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R²⁰, R³⁰ and X¹ to X⁴ includes a phenyl group, a naphthylgroup, an anthracenyl group and the like, and specific examples thereofinclude, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group,a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylylgroup, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, apentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, aisopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, atert-butylphenyl group, a n-pentylphenyl group, a neopentylphenyl group,a n-hexylphenyl group, a n-octylphenyl group, a n-decylphenyl group, an-dodecylphenyl group, a n-tetradecylphenyl group, a naphthyl group, andan anthracenyl group. Furthermore, the above substituents which aresubstituted, for example, with halogen atom(s), more specifically withfluorine atom(s), are exemplified. As preferable aryl group, a phenylgroup is exemplified.

The optionally substituted C₇₋₂₀ aralkyl group includes a benzyl group,a naphthylmethyl group, an anthracenylmethyl group, a diphenylmethylgroup and the like, and specific examples thereof include, for example,a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methylgroup, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methylgroup, a (2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methylgroup, a (2,6-dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methylgroup, a (2,3,4-trimethylphenyl)methyl group, a(2,3,5-trimethylphenyl)methyl group, a (2,3,6-trimethylphenyl)methylgroup, a (3,4,5-trimethylphenyl)methyl group, a(2,4,6-trimethylphenyl)methyl group, a (2,3,4,5-tetramethylphenyl)methylgroup, a (2,3,4,6-tetramethylphenyl)methyl group, a(2,3,5,6-tetramethylphenyl)methyl group, a (pentamethylphenyl)methylgroup, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an(isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a(sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a(n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a(n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a(n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, anaphthylmethyl group, an anthracenylmethyl group, a diphenylmethylgroup, and the above substituents substituted by halogen, morespecifically, a fluorine-substituted aralkyl group. A benzyl group isexemplified as a preferable substituent.

Specific examples of the optionally substituted C₁₋₁₀ alkoxy group forthe substituents R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ include a methoxygroup, an ethoxy group, a n-propoxy group, an isopropoxy group; an-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxygroup, a neopentyloxy group, a n-hexyloxy group, a n-octyloxy group, an-nonyloxy group, and a n-decyloxy group. Furthermore, the alkoxy groupssubstituted with halogen(s) are exemplified, and more specifically, afluorine atom-substituted alkoxy group, in which the alkoxy group issubstituted with fluorine atom(s), is exemplified. Preferably, a methoxygroup, an ethoxy group, and a tert-butoxy group are exemplified.

The optionally substituted C₆₋₂₀ aryloxy group for the substituents R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and X¹ to X⁴ includes a phenoxy group, anaphthoxy group, and an anthracenoxy group. Furthermore, specificexamples thereof include a phenoxy group, a 2-methylphenoxy group, a3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxygroup, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a2,6-dimethylphenoxy group, a 3,4-dimethylphenoxy group, a3,5-dimethylphenoxy group, a 2,3,4-trimethylphenoxy group, a2,3,5-trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, a2,3,4,6-tetramethylphenoxy group, a 2,3,5,6-tetramethylphenoxy group, apentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxygroup, an isopropylphenoxy group, a n-butylphenoxy group, asec-butylphenoxy group, a tert-butylphenoxy group, a n-hexylphenoxygroup, a n-octylphenoxy group, a n-decylphenoxy group, an-tetradecylphenoxy group, a naphthoxy group, an anthracenoxy group, andthe above substituents substituted with halogen atom(s), and morespecifically, a fluorine-substituted aryloxy group is exemplified.

The optionally substituted C₇₋₂₀ aralkyloxy group for the substituentsR², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and X¹ to X⁴ includes a benzyloxy group,a naphthylmethoxy group, an anthracenylmethoxy group, and adiphenylmethoxy group. Furthermore, specific examples thereof include,for example, a benzyloxy group, a (2-methylphenyl)methoxy group, a(3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a(2,3-dimethylphenyl)methoxy group, a (2,4-dimethylphenyl)methoxy group,a (2,5-dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxygroup, a (3,4-dimethylphenyl)methoxy group, a(2,3,4-trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxygroup, a (2,3,6-trimethylphenyl)methoxy group, a(3,4,5-trimethylphenyl)methoxy group, a (2,4,6-trimethylphenyl)methoxygroup, a (2,3,4,5-tetramethylphenyl)methoxy group, a(2,3,4,6-tetramethylphenyl)methoxy group, a(2,3,5,6-tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxygroup, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group,an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a(sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a(n-pentylphenyl)methoxy group, a (neopentylphenyl)methoxy group, a(n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a(n-decylphenyl)methoxy group, a (n-dodecylphenyl)methoxy group, anaphthylmethoxy group, an anthracenylmethoxy group, a diphenylmethoxygroup and the above substituents substituted with halogen(s), and morespecifically, a fluorine atom-substituted aralkyloxy group isexemplified. A benzyloxy group is exemplified as a preferablesubstituent.

The C₁₋₂₀ hydrocarbon-substituted silyl group for the substituents R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R³ is a silyl group substituted withC₁₋₂₀ hydrocarbon group(s). The hydrocarbon group as used hereinincludes, for example, C₁₋₁₀ alkyl groups such as a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a tert-butyl group, a n-pentyl group, a neopentylgroup, an amyl group, a n-hexyl group, a cyclohexyl group, a n-octylgroup, a n-decyl group and the like, and C₆₋₂₀ aryl groups such as aphenyl group, a tolyl group, a xylyl group, a naphthyl group, ananthracenyl group and the like. Such C₁₋₂₀ hydrocarbon-substituted silylgroup includes, for example, mono-substituted silyl groups such as amethylsilyl group, an ethylsilyl group, a phenylsilyl group and thelike, di-substituted silyl groups such as a dimethylsilyl group, adiethylsilyl group, a diphenylsilyl group and the like, tri-substitutedsilyl groups such as a trimethylsilyl group, a triethylsilyl group, atri-n-propylsilyl group, a tri-isopropylsilyl group, a tri-n-butylsilylgroup, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, atri-isobutylsilyl group, a tert-butyldimethylsilyl group, atri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilylgroup, a triphenylsilyl group and the like, preferably a trimethylsilylgroup, a tert-butyldimethylsilyl group, and a triphenylsilyl group.Furthermore, the above substituted silyl groups in which the hydrocarbongroups are substituted with halogen atom(s), e.g., fluorine atom(s), areexemplified.

The C₁₋₂₀ hydrocarbon-substituted amino group for the substituents R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and X¹ to X⁴ is an amino group substitutedwith two hydrocarbon groups. The hydrocarbon group as used hereinincludes, for example, C₁₋₁₀ alkyl groups such as a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a tert-butyl group, a n-pentyl group, a neopentylgroup, an amyl group, a n-hexyl group, a cyclohexyl group, a n-octylgroup, a n-decyl group and the like, and C₆₋₂₀ aryl groups such as aphenyl group, a tolyl group, a xylyl group, a naphthyl group, ananthracenyl group and the like. Such C₁₋₂₀ hydrocarbon-substituted aminogroup includes, for example, a dimethylamino group, a diethylaminogroup, a di-n-propylamino group, a diisopropylamino group, adi-n-butylamino group, a di-sec-butylamino group, a di-tert-butylaminogroup, a di-isobutylamino group, a tert-butylisopropylamino group, adi-n-hexylamino group, a di-n-octylamino group, a di-n-decylamino group,a diphenylamino group and the like, preferably, a dimethylamino groupand a diethylamino group.

The halogen atom for the substituents R⁶, R⁷, R¹, R⁹ and X¹ to X⁴includes a fluorine atom, a chlorine atom, a bromine atom and an iodineatom, preferably a fluorine atom and a chlorine atom.

In the formula (I), R²⁰ represents the same substituents as R¹, andspecific examples thereof include those exemplified for R¹. R³⁰represents the same substituents as R¹, and specific examples thereofinclude those exemplified for R¹. Furthermore, R³⁰ includes the samegroups as the silyl group substituted with optionally substituted C₁₋₂₀hydrocarbon group(s) for R² to R⁵.

Hereinafter the transition metal complex represented by the formula (I)is exemplified.

A Group 4 transition metal represented by M includes transition metalsof Group 4 in the periodic table of elements (IUPAC inorganic chemistrynomenclature, revised version, 1989), and for example, a titanium atom,a zirconium atom, a hafnium atom and the like are exemplified,preferably a titanium atom and a zirconium atom.

A Group 16 element represented by A includes, for example, an oxygenatom, a sulfur atom, a selenium atom and the like are exemplified, andas a preferable element, a oxygen atom is exemplified.

Atoms of Group 15 in the periodic table of elements represented by A¹and A² include, for example, a nitrogen atom, a phosphorus atom, anarsenic atom and the like, preferably a nitrogen atom.

In a transition metal complex according to the formula (I), R², R³, R⁴and R⁵ are preferably each a hydrogen atom or a C₁₋₅ alkyl group.

X¹ and X² preferably include a halogen atom, a C₁₋₁₀ alkyl group, aC₇₋₂₀ aralkyl group, a C₆₋₂₀ aryl group or a C₁₋₂₀hydrocarbon-substituted amino group, and more preferably, a halogen atomand a C₁₋₁₀ hydrocarbon-substituted amino group are exemplified.

As a transition metal complex according to the formula (I), those inwhich X¹ and X² are each a halogen atom or a C₁₋₁₀hydrocarbon-substituted amino group, R², R³, R⁴ and R⁵ are each a methylgroup, and R⁶, R⁷, R⁸ and R⁹ are each a hydrogen atom are preferred.

As a transition metal complex represented by the formula (I), transitionmetal complexes represented by the following formulas (I-1), (I-2),(I-3) and (I-4) are exemplified.

A transition metal complex represented by the formula (I) wherein —Y— is(a), the formula (I-1):

wherein R¹ to R⁹, R²⁰, X¹, X², M and A have the same meaning as definedin the above-mentioned formula (I), is hereinafter explained.

In Chem. Commun., 1999, 1405-1406,1-(2-methylinden-1-yl)-2-naphthylmethyloxyzirconiumbisdiethylamide isdisclosed, however, its function as a polymerization catalyst is notdisclosed and suggested at all.

In said transition metal complex, at least one of R¹ and R²⁰ preferablyrepresents an optionally substituted C₁₋₁₀ alkyl-group, an optionallysubstituted C₆₋₂₀ aryl group or an optionally substituted C₇₋₂₀ aralkylgroup.

Specific compounds represented by the formula (I-1) include thefollowing compounds: 2-(cyclopentadienyl)benzyloxytitanium dichloride,2-(2-methylcyclopentadienyl)benzyloxytitanium dichloride,2-(3-methylcyclopentadienyl)benzyloxytitanium dichloride,2-(2,3-dimethylcyclopentadienyl)benzyloxytitanium dichloride,2-(2,4-dimethylcyclopentadienyl)benzyloxytitanium dichloride,2-(2,3,4-trimethylcyclopentadienyl)benzyloxytitanium dichloride,2-(2,3,5-trimethylcyclopentadienyl)benzyloxytitaniudium dichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitanium dichloride,2-(2-dimethylaminomethylcyclopentadienyl)benzyloxytitanium dichloride,2-(3-dimethylaminomethylcyclopentadienyl)benzyloxytitanium dichloride,2-(inden-1-yl)benzyloxytitanium dichloride,2-(2-phenylinden-1-yl)benzyloxytitanium dichloride,2-(fluoren-1-yl)benzyloxytitanium dichloride,2-(cyclopentadienyl)-1-naphthylmethyloxytitanium dichloride,2-(2-methylcyclopentadienyl)-1-naphthylmethyloxytitanium dichloride,2-(3-methylcyclopentadienyl)-1-naphthylmethyloxytitanium dichloride,2-(2,3-dimethylcyclopentadienyl)-1-naphthylmethyloxytitanium dichloride,2-(2,4-dimethylcyclopentadienyl)-1-naphthylmethyloxytitanium dichloride,2-(2,3,4-trimethylcyclopentadienyl)-1-naphthylmethyloxytitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-1-naphthylmethyloxytitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthylmethyloxytitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthylmethyloxytitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthylmethyloxytitaniumdichloride, 2-(inden-1-yl)-1-naphthylmethyloxytitanium dichloride,2-(2-phenylinden-1-yl)-1-naphthylmethyloxytitanium dichloride,2-(fluoren-1-yl)-1-naphthylmethyloxytitanium dichloride,1-[2-(cyclopentadienyl)phenyl]ethyloxytitanium dichloride,1-[2-(2-methylcyclopentadienyl)phenyl]ethyloxytitanium dichloride,1-[2-(3-methylcyclopentadienyl)phenyl]ethyloxytitanium dichloride,1-[2-(2,3-dimethylcyclopentadienyl)phenyl]ethyloxytitanium dichloride,1-[2-(2,4-dimethylcyclopentadienyl)phenyl]ethyloxytitanium dichloride,1-[2-(2,3,4-trimethylcyclopentadienyl)phenyl]ethyloxytitaniumdichloride,1-[2-(2,3,5-trimethylcyclopentadienyl)phenyl]ethyloxytitaniumdichloride,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]ethyloxytitaniumdichloride,1-[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]ethyloxytitaniumdichloride,1-[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]ethyloxytitaniumdichloride, 1-[2-(inden-1-yl)phenyl]ethyloxytitanium dichloride,1-[2-(2-phenylinden-1-yl)phenyl]ethyloxytitanium dichloride,1-[2-(fluoren-1-yl)phenyl]ethyloxytitanium dichloride,1-[2-(cyclopentadienyl)-1-naphthyl]ethyloxytitanium dichloride,1-[2-(2-methylcyclopentadienyl)-1-naphthyl]ethyloxytitanium dichloride,1-[2-(3-methylcyclopentadienyl)-1-naphthyl]ethyloxytitanium dichloride,1-[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride,1-[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]ethyloxytitaniumdichloride, 1-[2-(inden-1-yl)-1-naphthyl]ethyloxytitanium dichloride,1-[2-(2-phenylinden-1-yl)-1-naphthyl]ethyloxytitanium dichloride,1-[(2-(fluoren-1-yl)-1-naphthyl]ethyloxytitanium dichloride,1-[2-(cyclopentadienyl)phenyl]-1-methyl-ethyloxytitanium dichloride,1-[2-(2-methylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(3-methylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[(2-(2,3-dimethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,4-dimethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,3,5-trimethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]-1-methyl-ethyloxytitaniumdichloride, 1-[2-(inden-1-yl)phenyl]-1-methyl-ethyloxytitaniumdichloride, 1-[2-(2-phenylinden-1-yl)phenyl]-1-methyl-ethyloxytitaniumdichloride, 1-[2-(fluoren-1-yl)phenyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(cyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2-methylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[(2-(3-methylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride, 1-[2-(inden-1-yl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride,1-[2-(2-phenylinden-1-yl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride, 1-[2-(fluoren-1-yl)-1-naphthyl]-1-methyl-ethyloxytitaniumdichloride, [2-(cyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2-methylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(3-methylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]-t-butyl-methyloxyoxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]-t-butyl-methyloxytitaniumdichloride, [2-(inden-1-yl)phenyl]-t-butyl-methyloxytitanium dichloride,[2-(2-phenylinden-1-yl)phenyl]-t-butyl-methyloxytitanium dichloride,[2-(fluoren-1-yl)phenyl]-t-butyl-methyloxytitanium dichloride,[2-(cyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitanium dichloride,[2-(2-methylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(3-methylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)-1′-naphthyl]-t-butyl-methyloxytitaniumdichloride, [2-(inden-1-yl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride,[2-(2-phenylinden-1-yl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride, [2-(fluoren-1-yl)-1-naphthyl]-t-butyl-methyloxytitaniumdichloride, [2-(cyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride, [2-(2-methylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride, [2-(3-methylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]phenylmethyloxyoxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]phenylmethyloxytitaniumdichloride, [2-(inden-1-yl)phenyl]phenylmethyloxytitanium dichloride,[2-(2-phenylinden-1-yl)phenyl]phenylmethyloxytitanium dichloride,[2-(fluoren-1-yl)phenyl]phenylmethyloxytitanium dichloride,[2-(cyclopentadienyl)-1-naphthyl]phenylmethyloxytitanium dichloride,[2-(2-methylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(3-methylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]phenyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]phenylmethyloxytitaniumdichloride, [2-(inden-1-yl)-1-naphthyl]phenylmethyloxytitaniumdichloride, [2-(2-phenylinden-1-yl)-1-naphthyl]phenylmethyloxytitaniumdichloride, [2-(fluoren-1-yl)-1-naphthyl]phenylmethyloxytitaniumdichloride, [2-(cyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2-methylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(3-methylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]diphenylmethyloxyoxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]diphenylmethyloxytitaniumdichloride, [2-(inden-1-yl)phenyl]diphenylmethyloxytitanium dichloride,[2-(2-phenylinden-1-yl)phenyl]diphenylmethyloxytitanium dichloride,[2-(fluoren-1-yl)phenyl]diphenylmethyloxytitanium dichloride,[2-(cyclopentadienyl)-1-naphthyl]diphenylmethyloxytitanium dichloride,[2-(2-methylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(3-methylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]diphenyloxytitaniumdichloride,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride,[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]diphenylmethyloxytitaniumdichloride, [2-(inden-1-yl)-1-naphthyl]diphenylmethyloxytitaniumdichloride, [2-(2-phenylinden-1-yl)-1-naphthyl]diphenylmethyloxytitaniumdichloride, [2-(fluoren-1-yl)-1-naphthyl]diphenylmethyloxytitaniumdichloride and the like. Similarly, the above-mentioned compounds inwhich (2-cyclopentadienyl-1-naphthyl) is changed to(2-cyclopentadienyl-3-naphthyl), in which (inden-1-yl) is changed to(inden-2-yl), in which titanium is changed to zirconium or hafnium, orin which dichloride is changed to dibromide, diiodide, dimethoxide,diisopropoxide, dibutoxide, bisdimethylamide, bisdiethylamide, dimethylor bistrimethylsilylmethyl, and the like are also exemplified.

The transition metal complex represented by the formula (I) wherein —Y—is (b), the formula (I-2):

is hereinafter explained.

In the formula (I-2), A¹ is preferably a nitrogen atom.

-   -   R², R³, R⁴ and R⁵ are preferably each a hydrogen atom or a C₁₋₅        alkyl group.

Specific examples of the transition metal complex represented by theformula (I-2) include the following compounds:

N-[(2-(cyclopentadienyl)phenyl)methyl]-N-phenylamidotitanium dichloride,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-phenylamidotitaniumdichloride, N-[(2-(inden-1-yl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-phenylamidotitaniumdichloride, N-[(2-(fluoren-1-yl)phenyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)titaniumdichloride,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(inden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(fluoren-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl])-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride, N-[(2-(inden-1-yl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride, N-[(2-(fluoren-1-yl)phenyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-n-butylamidotitaniumdichloride, N-[(2-(inden-1-yl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-n-butylaimidotitaniumdichloride, N-[(2-(fluoren-1-yl)phenyl)methyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-phenylamidotitaniumdichloride, N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-phenylamidotitaniumdichloride, N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride, N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride, N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride, N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-phenylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)aimidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylaimidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-tert-butylamidotitaniumdichloride,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl)]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-n-butylamidotitaniumdichloride,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride, N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-phenylamidotitaniumdichloride,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-phenylamidotitanium,dichloride,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amidotitaniumdichloride,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-tert-butylamidotitaniumdichloride,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride, N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-n-butylamidotitaniumdichloride and the like.

Similarly, the above-mentioned compounds in which(2-cyclopentadienyl-1-naphthyl) is changed to(2-cyclopentadienyl-3-naphthyl), in which (inden-1-yl) is changed to(inden-2-yl), in which titanium is changed to zirconium or hafnium, orin which dichloride is changed to dibromide, diiodide, dimethoxide,diisopropoxide, dibutoxide, bisdimethylamide, bisdiethylamide, dimethylor bistrimethylsilylmethyl, and the like are also exemplified.

The transition metal complex represented by the formula (I) wherein —Y—is (d), the formula (I-3):

is hereinafter explained.

In the formula (I-3), A¹ and A² are preferably both nitrogen atoms.

Specific examples of the transition metal complex represented by theformula (I-3) include compounds obtained by reacting compoundsexemplified as hydrazone compounds of the formula (7) described belowwith transition metal compounds represented by the formula (III).

The transition metal complex represented by the formula (I) wherein —Y—is (c), the formula (I-4):

is hereinafter explained.

In the formula (I-4), A is preferably a nitrogen atom.

Specific examples of the transition metal complex represented by theformula (I-4) include the following compounds:

2-(cyclopentadienyl)-α-tert-butyl-benzenemethanimidotitanium dichloride,2-(2-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride, 2-(cyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzehemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride, 2-(2-methylinden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride, 2-(2-phenylinden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride, 2-(cyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2,3,4-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride, 2-(2-methylinden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride, 2-(2-phenylinden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,2-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride, 2-(cyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(fluoren-1-yl)-α-tert-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-n-butyl-1-naphthalenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride, 2-(fluoren-1-yl)-α-phenyl-1-naphthalenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3′,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimidotitaniumdichloride,2-(cyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-methylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride, 2-(inden-1-yl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-methylinden-1-yl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(2-phenylinden-1-yl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,2-(fluoren-1-yl)-α-cyclohexyl-1-naphthalenemethanimidotitaniumdichloride,3-(cyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-methylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride, 3-(inden-1-yl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylinden-1-yl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-phenylinden-1-yl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(fluoren-1-yl)-α-tert-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(cyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-methylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3-dimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,4-dimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride, 3-(inden-1-yl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylinden-1-yl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-phenylinden-1-yl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride, 3-(fluoren-1-yl)-α-n-butyl-2-naphthalenemethanimidotitaniumdichloride,3-(cyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-methylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3-dimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,4-dimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride, 3-(inden-1-yl)-1-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylinden-1-yl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-phenylinden-1-yl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride, 3-(fluoren-1-yl)-α-phenyl-2-naphthalenemethanimidotitaniumdichloride,3-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimidotitaniumdichloride,3-(cyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-methylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride, 3-(inden-1-yl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-methylinden-1-yl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(2-phenylinden-1-yl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-(fluoren-1-yl)-α-cyclohexyl-2-naphthalenemethanimidotitaniumdichloride,3-dimethylamino-6-(cyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butylbenzenemethanimidotitanium dichloride,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(inden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylinden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-phenylinden-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(fluoren-1-yl)-α-tert-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(cyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(inden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylinden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-phenylinden-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(fluoren-1-yl)-α-n-butyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(cyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(inden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylinden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-phenylinden-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(fluoren-1-yl)-α-phenyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,6-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(cyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(inden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-methylinden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(2-phenylinden-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride,3-dimethylamino-6-(fluoren-1-yl)-α-cyclohexyl-benzenemethanimidotitaniumdichloride and the like. Similarly, the above-mentioned compounds inwhich (2-cyclopentadienyl-1-naphthyl) is changed to(2-cyclopentadienyl-3-naphthyl), in which (inden-1-yl) is changed to(inden-2-yl), in which titanium is changed to zirconium or hafnium, orin which dichloride is changed to dibromide, diiodide, dimethoxide,diisopropoxide, dibutoxide, bisdimethylamide, bisdiethylamide, dimethylor bistrimethylsilylmethyl, and the like are also exemplified.

The transition metal complex (I) of the present invention is generallyused as a polymerization catalyst in combination with the compoundselected from the above-mentioned A1 to A3.

Hereinafter A1 to A3 are explained.

Specific examples of the organic aluminum compound (A1) represented bythe formula E1_(a)Al(Z)_((3-a)) include, for example, trialkylaluminumsuch as trimethylaluminum, triethylaluminum, tripropylaluminum,triisobutylaluminum, trihexylaluminum and the like; dialkylaluminumchloride such as dimethylaluminum chloride, diethylaluminum chloride,dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminumchloride and the like; alkylaluminum dichloride such as methylaluminumdichloride, ethylaluminum dichloride, propylaluminum dichloride,isobutylaluminum dichloride, hexylaluminum dichloride and the like; anddialkylaluminum hydride such as dimethylaluminum hydride,diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, dihexylaluminum hydride and the like. Preferablytrialkylaluminum is exemplified, and more preferably, triethylaluminumand triisobutylaluminum are exemplified.

Specific examples of E2 and E3 for the cyclic aluminoxane (A2) havingthe structure represented by the formula {—Al(E2)-O—}_(b) and the linearaluminoxane (A3) having the structure represented by the formulaE3{—Al(E3)-O—}_(c)Al(E3)₂ include alkyl groups (preferably C₁-C₅ alkylgroups) such as a methyl group, an ethyl group, a normal propyl group,an isopropyl group, a normal butyl group, an isobutyl group, a normalpentyl group, a neopentyl group and the like b is an integer of not lessthan 2, and c is an integer of not less than 1. Preferably, E2 and E3are each a methyl group or an isobutyl group, b is 2 to 40, and c is 1to 40.

The above-mentioned aluminoxanes are prepared by various methods, whichmethods are not specifically limited, and may be prepared according toknown methods. For example, trialkylaluminum (e.g., trimethylaluminumand the like) is dissolved in a suitable organic solvent (e.g., benzene,aliphatic hydrocarbon and the like) and then the solution is contactedwith water to prepare aluminoxane. A method for preparation ofaluminoxane comprising contacting trialkylaluminum (e.g.,trimethylaluminum and the like) to a metal salt containing crystal water(e.g., copper sulfate hydrate and the like) can be also exemplified.

Specifically, methylaluminoxane (MAO) and the like are exemplified.Furthermore, MMAO (Modified methyl aluminoxane) obtained by modifyingmethylaluminoxane by addition of triisobutylaluminum is exemplified. Theamount of triisobutylaluminum to be used for obtaining MMAO may be aneffective amount in modifying methylaluminoxane and is not specificallylimited. Alternatively, aluminoxane to be used in the present inventionmay be a commercial available product.

The combination of the transition metal complex of the present inventionand a compound selected from A1 to A3 can be used further in combinationwith a compound (B) as a polymerization catalyst.

Hereinafter the compounds (B1), (B2) and (B3) used in the presentinvention are explained.

In the boron compound (B1) represented by the formula BQ₁Q₂Q₃, B is aboron atom in a trivalent valence state, and Q₁ to Q₃ may be the same ordifferent and each is a halogen atom, a hydrocarbon group containing 1to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms,an alkoxy group containing 1 to 20 carbon atoms or a di-substitutedamino group containing 2 to 20 carbon atoms. Specifically, Q₁ to Q₃include the same substituents as those exemplified for R¹ to R⁹.Preferably, Q₁ to Q₃ are each a halogen atom, a hydrocarbon groupcontaining 1 to 20 carbon atoms, or a halogenated hydrocarbon groupcontaining 1 to 20 carbon atoms.

Specific examples of (B1) include tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane,phenylbis(pentafluorophenyl)borane and the like, more preferablytris(pentafluorophenyl)borane.

In the boron compound (B2) represented by the formula Z⁺(BQ₁Q₂Q₃Q₄)⁻, Z⁺is an inorganic or organic cation, B is a boron atom in a trivalentvalence state, and Q₁ to Q₄ have the same meaning as the Q₁ to Q₃ in theabove-mentioned (B1).

For specific examples of the compound represented by the formulaZ⁺(BQ₁Q₂Q₃Q₄)⁻, Z⁺ includes a ferrocenium cation, an alkyl-substitutedferrocenium cation, a silver cation and the like as an inorganic cation,and a triphenylmethyl cation and the like as an organic cation. As the(BQ₁Q₂Q₃Q₄)⁻, tetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenylbis(pentafluorophenyl)borate,tetrakis(3,5-bistrifluoromethylphenyl)borate and the like areexemplified.

Specific combinations of the Z⁺ and the (BQ₁Q₂Q₃Q₄)⁻ include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate and the like, and morepreferably triphenylmethyl tetrakis(pentafluorophenyl)borate.

Furthermore, in the boron compound represented by the formula(L-H)⁺(BQ₁Q₂Q₃Q₄)⁻, L is a neutral Lewis base, (L-H)⁺ is a Brønstedacid, B is a boron atom in a trivalent valence state, and Q₁ to Q₄ arethe same as the Q₁ to Q₃ in the above-mentioned (B1).

For specific examples of the compound represented by the formula(L-H)⁺(BQ₁Q₂Q₃Q₄)⁻, the Brønsted acid (L-H)⁺ includestrialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium,triarylphosphonium and the like, and the (BQ₁Q₂Q₃Q₄)⁻ includes those asdescribed above.

Specific combinations of the (L-H)⁺ and the (BQ₁Q₂Q₃Q₄) includetriethylammonium tetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(normal butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(normal butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate and the like, and most preferably,tri(normal butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and the like.

In addition to the transition metal complex represented by the formula(I) and the compound (A), or a combination thereof, the compound (B) canbe used as a catalyst component to carry out polymerization reaction.Into the polymerization reaction, these catalyst components may be addedin any order. Alternatively, components optionally selected from thecatalyst components used in a combination as described above arepreviously contacted with each other and the reaction product thusobtained can also be used in the polymerization reaction.

The amount of each catalyst component to be used is preferably 0.1 to10,000, more preferably 5 to 2000 in the mole ratio of compound(A)/transition metal complex, and preferably 0.01 to 100, morepreferably 0.5 to 10 in the mole ratio of compound (B)/transition metalcomplex. The concentration of each catalyst component, if it is used ina solution state, is preferably 0.0001 to 5 mmol/L, more preferably0.001 to 1 mmol/L for the transition metal complex represented by theformula (I); preferably 0.01 to 500 mmol/L, more preferably 0.1 to 100mmol/L (as converted to Al atom) for the compound (A); and preferably0.0001 to 5 mmol/L, more preferably 0.001 to 1 mmol/L for the compound(B).

In the present invention, as a monomer used for polymerization, olefins,diolefins and the like consisting of 2 to 20 carbon atoms can be used,and two or more monomers can be used simultaneously. Such monomers areexemplified hereinafter, but the present invention is not limited to thefollowing compounds. Specific examples of such olefin include ethylene,propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,decene-1,5-methyl-2-pentene-1, vinylcyclohexene and the like. Thediolefin compound includes conjugated dienes of hydrocarbon compoundsand non-conjugated dienes. Specific examples of such diene compoundsinclude, as specific examples of the non-conjugated diene compound,1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene,5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene,5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene,1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene and the like,and as specific examples of the conjugated diene compound,1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene,1,3-cyclooctadiene, 1,3-cyclohexadiene and the like.

Specific examples of monomers constituting a copolymer include, but notlimited to, ethylene and propylene, ethylene and butene-1, ethylene andhexene-1, propylene and butene-1, and a combination of the above anycombination and 5-ethylidene-2-norbornene.

In the present invention, aromatic vinyl compounds can be also used as amonomer. Specific examples of the aromatic vinyl compound includestyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene,o-chlorostyrene, p-chlorostyrene, α-methylstyrene, divinylbenzene andthe like.

The method for polymerization is not specifically limited, and forexample, may be solvent polymerization or slurry polymerization, inwhich aliphatic hydrocarbon such as butane, pentane, hexane, heptane oroctane, aromatic hydrocarbon such as benzene or toluene, or halogenatedhydrocarbon such as methylene dichloride is used as a solvent, or gasphase polymerization in a gaseous monomer, which may be eithersuccessive polymerization or batch polymerization.

The polymerization temperature can be generally in the range of −50° C.to 200° C., specifically preferably in the range of −20° C. to 100° C.The polymerization pressure is preferably ordinary pressure to 60kg/cm²G (6 MPa). The polymerization period is generally suitablydetermined depending on the kind of an objective polymer and reactionapparatus and can be in the range of 1 min to 20 hrs. In the presentinvention, a chain transfer agent such as hydrogen can be also added tothe polymerization reaction in order to adjust the molecular weight of acopolymer.

Next, the substituted cyclopentadiene ligand represented by the formula(II) is explained.

As the compounds represented by the formula (II), the compoundsrepresented by the following formulas (5), (6) and (7) are exemplified.

A substituted cyclopentadiene compound represented by the formula (5):

wherein R¹ to R⁹ and R²⁰ have the same meanings as above; provided thatneither R² and R³ nor R⁴ and R⁵ are linked to each other and takentogether with the cyclopentadiene ring to form a fluorene ring or anindenyl ring, is explained below.

In Tetrahedron Letters, 39 (1998), 6537-6576,1-(2′-methyl-3′-indenyl)-2-naphthalenemethanol and1-(3′-indenyl)-2-naphthalenemethanol are disclosed, but polymerizationcatalysts comprising these compounds as a ligand are not disclosed andsuggested at all. Furthermore, 9-(2-hydroxymethyl-1-naphthyl)fluorene,9-[2-α-hydroxybenzyl)-1-naphthyl]fluorene and9-[2-(α-hydroxyethyl)-1-naphthyl]fluorene are disclosed in Bull. Chem.Soc. Jpn., 55, 3267-3272 (1982) and9-[2-(1-hydroxy-2-trimethylsilylethyl)-1-naphthyl]fluorene is disclosedin Bull. Chem. Soc. Jpn., 62, 621-623 (1989). However, each of thesearticles fails to disclose or suggest polymerization catalystscomprising these compounds as a ligand.

The compound of the formula (5) can be produced by reacting the carbonylcompound of formula (1) with a nucleophilic agent.

A nucleophilic agent used in such reaction includes, for example,hydride compounds and carbanion compounds (R²⁰Li or R²⁰MgX or metalhydride compounds). Such a nucleophilic agent includes sodium hydride,lithium aluminum hydride, methylmagnesium bromide, ethylmagnesiumbromide, phenylmagnesium bromide, n-butylmagnesium bromide,t-butylmagnesium bromide, methyllithium, phenyllithium, t-butyllithiumand the like. Similarly, the above-mentioned compounds in whichmagnesium bromide is changed to magnesium chloride or magnesium iodideare also exemplified.

The reaction is generally carried out in an inert solvent to reaction.Such a solvent includes, for example, aprotic solvents such as aromatichydrocarbon solvents such as benzene and toluene and the like; aliphatichydrocarbon solvents such as hexane, heptane and the like; ethersolvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and thelike; amide solvents such as hexamethylphosphoric amide,dimethylformamide and the like; polar solvents such as acetonitrile,propionitrile, acetone, diethyl ketone, methyl isobutyl ketone,cyclohexanone and the like; and halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene and thelike. One or a mixture of two or more of the solvents is used. Theamount of a solvent to be used is usually in the range of 1 to 200times, preferably 3 to 50 times the weight of the carbonyl compoundrepresented by the formula (1).

The reaction temperature is usually in the range of −100° C. to theboiling point of a solvent, preferably −80 to 120° C.

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer cannot beeasily separated due to use of a solvent compatible with water or use ofa small amount of a solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate or chlorobenzene to the reaction mixture. Thecyclopentadiene represented by the formula (5) can be purified, forexample, by washing said solution of the compound with water, dryingsaid solution, and then distilling off the solvent and further bymethods such as recrystallization, distillation, column chromatographytreatment and the like.

Specific examples of the compound of the formula (5) thus obtainedinclude the following compounds:

2-(cyclopentadienyl)benzylalcohol,2-(2-methylcyclopentadienyl)benzylalcohol,2-(3-methylcyclopentadienyl)benzylalcohol,2-(2,3-dimethylcyclopentadienyl)benzylalcohol,2-(2,4-dimethylcyclopentadienyl)benzylalcohol,2-(2,3,4-trimethylcyclopentadienyl)benzylalcohol,2-(2,3,5-trimethylcyclopentadienyl)benzylalcohol,2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol,2-(2-dimethylaminomethylcyclopentadienyl)benzylalcohol,2-(3-dimethylaminomethylcyclopentadienyl)benzylalcohol,2-(cyclopentadienyl)-1-naphthylmethylalcohol,2-(2-methylcyclopentadienyl)-1-naphthylmethylalcohol,2-(3-methylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2,3-dimethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2,4-dimethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2,3,4-trimethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2,3,5-trimethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthylmethylalcohol,2-(fluoren-1-yl)-1-naphthylmethylalcohol,1-[2-(cyclopentadienyl)phenyl]ethylalcohol,1-[2-(2-methylcyclopentadienyl)phenyl]ethylalcohol,1-[(2-(3-methylcyclopentadienyl)phenyl]ethylalcohol,1-[(2-(2,3-dimethylcyclopentadienyl)phenyl]ethylalcohol,1-[2-(2,4-dimethylcyclopentadienyl)phenyl]ethylalcohol,1-[2-(2,3,4-trimethylcyclopentadienyl)phenyl]ethylalcohol,1-[2-(2,3,5-trimethylcyclopentadienyl)phenyl]ethylalcohol,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]ethylalcohol,1-[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]ethylalcohol,1-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl]ethylalcohol,1-[(2-(cyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2-methylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(3-methylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]ethylalcohol,1-[2-(cyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2-methylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[(2-(3-methylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2,3-dimethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2,4-dimethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2,3,4-trimethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2,3,5-trimethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl]-1-methyl-ethylalcohol,1-[2-(cyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2-methylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(3-methylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,1-[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-1-methyl-ethylalcohol,[2-(cyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2-methylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(3-methylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2,3-dimethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2,4-dimethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]-t-butyl-methyloxyalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]-t-butyl-methylalcohol,[2-(cyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2-methylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(3-methylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]-t-butyl-methylalcohol,[2-(cyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2-methylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(3-methylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2,3-dimethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2,4-dimethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]phenylmethyloxyalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]phenylmethylalcohol,[2-(cyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2-methylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(3-methylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]phenylalcohol,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]phenylmethylalcohol,[2-(cyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2-methylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(3-methylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2,3-dimethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2,4-dimethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)phenyl]diphenylmethyloxyalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)phenyl]diphenylmethylalcohol,[2-(cyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2-methylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(3-methylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2,3-dimethylcyclopentadienyl)-1-naphthyl]diphenylalcohol,[2-(2,4-dimethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcohol,[2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl]diphenylmethylalcoholand the like.

The amine compound represented by the formula (6):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²⁰ and R³⁰ the samemeanings as defined for the above-mentioned formula (I-2), ishereinafter explained.

The amine compound of the formula (6) can be obtained by reducing animine compound represented by the formula (9):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸; R⁹ and R³⁰ have the samemeanings as defined for the formula (I-2); provided that R³⁰ is not ahydrogen atom, or reacting said compound with a nucleophilic agent.

A nucleophilic agent used in the reaction includes metal hydridecompounds, organic lithium compounds, organic magnesium compounds andthe like (R²⁰Li or R²⁰MgX; provided that R²⁰ is not a hydrogen atom).

Such a nucleophilic agent includes metal hydride compounds such aslithium aluminum hydride, sodium borohydride, sodium cyanoborohydrideand the like; methylmagnesium bromide, ethylmagnesium bromide,phenylmagnesium bromide, n-butylmagnesium bromide, t-butylmagnesiumbromide, methyllithium, phenyllithium, t-butyllithium and the like.Similarly, the above-mentioned compounds in which magnesium bromide ischanged to magnesium chloride or magnesium iodide are also exemplified.The amount of the nucleophilic agent to be used is usually about 0.25 to5 moles relative to 1 mole of the imine.

The above reaction is usually carried out in a solvent. Such a solventincludes, for example, alcohol solvents such as methanol, ethanol,isopropanol and the like; aprotic solvents such as aromatic hydrocarbonsolvents such as benzene, toluene and the like; aliphatic hydrocarbonsolvents such as hexane, heptane and the like; ether solvents such asdiethyl ether, tetrahydrofuran, 1,4-dioxane and the like; amide solventssuch as hexamethylphosphoric amide, dimethylformamide and the like;polar solvents such as acetonitrile, propionitrile, acetone, diethylketone, methyl isobutyl ketone, cyclohexanone and the like; andhalogenated solvents such as dichloromethane, dichloroethane,chlorobenzene, dichlorobenzene and the like. One or a mixture of two ormore of the solvents is used. The amount of a solvent to be used isusually in the range of 1 to 200 times, preferably 3 to 50 times theweight of the imine represented by the formula (9).

The reaction temperature is usually in the range of −100° C. to theboiling point of a solvent, preferably −80 to 120° C.

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer can not beeasily separated due to use of a solvent compatible with water or use ofa small amount of a solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate or chlorobenzene to the reaction mixture. Theamine represented by the formula (6) can be purified, for example, bywashing said solution of the compound with water, drying said solution,and then distilling off the solvent, and further by methods such asrecrystallization, distillation, column chromatography treatment and thelike.

The imine compound of the formula (9) can be produced by reacting thecarbonyl compound of the formula (1) with an amine compound (R³⁰—NH₂).

Specific examples of the imine compound of the formula

(9) include the following compounds:N-(2-(cyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2-methylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(3-methylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)methylene-N-phenylamine,N-(2-(inden-1-yl)phenyl)methylene-N-phenylamine,N-(2-(2-methylinden-1-yl)phenyl)methylene-N-phenylamine,N-(2-(2-phenylinden-1-yl)phenyl)methylene-N-phenylamine,N-(2-(cyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-methylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(inden-1-yl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylinden-1-yl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-phenylinden-1-yl)phenyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(cyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2-methylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(3-methylcyclopentadienyl)-phenyl)methylene-N-tert-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)methylene-N-tert-butylamine,N-(2-(inden-1-yl)phenyl)methylene-N-tert-butylamine,N-(2-(2-methylinden-1-yl)phenyl)methylene-N-tert-butylamine,N-(2-(2-phenylinden-1-yl)phenyl)methylene-N-tert-butylamine,N-(2-(cyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2-methylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(3-methylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)methylene-N-n-butylamine,N-(2-(inden-1-yl)phenyl)methylene-N-n-butylamine,N-(2-(2-methylinden-1-yl)phenyl)methylene-N-n-butylamine,N-(2-(2-phenylinden-1-yl)phenyl)methylene-N-n-butylamine,N-(2-(cyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2-methylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(3-methylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-phenylamine,N-(2-(inden-1-yl)phenyl)ethylidene-N-phenylamine,N-(2-(2-methylinden-1-yl)phenyl)ethylidene-N-phenylamine,N-(2-(2-phenylinden-1-yl)phenyl)ethylidene-N-phenylamine,N-(2-(cyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-methylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(inden-1-yl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylinden-1-yl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-phenylinden-1-yl)phenyl)ethylidene-N-(2,4,6-trimethylphenyl)amine,N-(2-(cyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2-methylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(3-methylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-tert-butylamine,N-(2-(inden-1-yl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2-methylinden-1-yl)phenyl)ethylidene-N-tert-butylamine,N-(2-(2-phenylinden-1-yl)phenyl)ethylidene-N-tert-butylamine,N-(2-(cyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2-methylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(3-methylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)phenyl)ethylidene-N-n-butylamine,N-(2-(inden-1-yl)phenyl)ethylidene-N-n-butylamine,N-(2-(2-methylinden-1-yl)phenyl)ethylidene-N-n-butylamine,N-(2-(2-phenylinden-1-yl)phenyl)ethylidene-N-n-butylamine,N-(2-(cyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2-methylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(3-methylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(3-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-phenylamine,N-(2-(inden-1-yl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2-methylinden-1-yl)-1-naphthyl)methylene-N-phenylamine,N-(2-(2-phenylinden-1-yl)-1-naphthyl)methylene-N-phenylamine,N-(2-(cyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-methylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(3-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(inden-1-yl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-methylinden-1-yl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(2-phenylinden-1-yl)-1-naphthyl)methylene-N-(2,4,6-trimethylphenyl)amine,N-(2-(cyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2-methylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(3-methylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(inden-1-yl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2-methylinden-1-yl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(2-phenylinden-1-yl)-1-naphthyl)methylene-N-tert-butylamine,N-(2-(cyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2-methylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(3-methylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(3-dimethylaminocyclopentadienyl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(inden-1-yl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2-methylinden-1-yl)-1-naphthyl)methylene-N-n-butylamine,N-(2-(2-phenylinden-1-yl)-1-naphthyl)methylene-N-n-butylamine and thelike.

Specific examples of the amine compound of the formula (6) thus obtainedinclude the following compounds:

N-[(2-(cyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-phenylamine,N-[(2-(inden-1-yl)phenyl)methyl]-N-phenylamine,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-phenylamine,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-phenylamine,N-[(2-(fluoren-1-yl)phenyl)methyl]-N-phenylamine,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)titaniumdichloride,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,5′-trimethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(inden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(fluoren-1-yl)phenyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-tert-butylamine,N-[(2-(inden-1-yl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-tert-butylamine,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-tert-butylamine,N-[(2-(fluoren-1-yl)phenyl)methyl]-N-tert-butylamine,N-[(2-(cyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2-methylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(3-methylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2,3-dimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2,4-dimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)methyl]-N-n-butylamine,N-[(2-(inden-1-yl)phenyl)methyl]-N-n-butylamine,N-[(2-(2-methylinden-1-yl)phenyl)methyl]-N-n-butylamine,N-[(2-(2-phenylinden-1-yl)phenyl)methyl]-N-n-butylamine,N-[(2-(fluoren-1-yl)phenyl)methyl]-N-n-butylamine,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-phenylamine,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-tert-butylamine,N-[1-(2-(cyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(inden-1-yl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(fluoren-1-yl)phenyl)ethyl]-N-n-butylamine,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-phenylamine,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-(2,4,6-trimethylphenyl)amine,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-tert-butylamine,N-[1-(2-(cyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(3-methylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2,3-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2,4-dimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2,3,4-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2,3,5-trimethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(3-dimethylaminomethylcyclopentadienyl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(inden-1-yl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2-methylinden-1-yl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(2-phenylinden-1-yl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(fluoren-1-yl)phenyl)-1-methylethyl]-N-n-butylamine,N-[1-(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-phenylamine,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-(2,4,6-trimethylphenyl)amine,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-tert-butylamine,N-[(2-(cyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2-methylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(3-methylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2,3-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2,4-dimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2,3,4-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2,3,5-trimethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(3-dimethylaminomethylcyclopentadienyl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(inden-1-yl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2-methylinden-1-yl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(2-phenylinden-1-yl)-1-naphthyl)methyl]-N-n-butylamine,N-[(2-(fluoren-1-yl)-1-naphthyl)methyl]-N-n-butylamine and the like.

The hydrazone compound represented by the formula (7):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R³⁰ have the samemeanings as defined for the above-mentioned formula (II), is hereinafterexplained.

The compound of the formula (7) can be produced by reacting the carbonylcompound of the formula (I) with a hydrazine compound (R³⁰—NHNH₂).

As the hydrazine compound, the following compounds are exemplified.

The hydrazine to be used in the reaction includes aromatic hydrazinessuch as phenylhydrazine, 2-methylphenylhydrazine,3-methylphenylhydrazine, 4-methylphenylhydrazine,2,4-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine,3,5-dimethylphenylhydrazine, 2,4,6-trimethylphenylhydrazine,2-isopropylphenylhydrazine, 3-isopropylphenylhydrazine,4-isopropylphenylhydrazine, 2,6-diisopropylphenylhydrazine,2-tert-butylphenylhydrazine, 4-tert-butylphenylhydrazine,2,4-di-tert-butylphenylhydrazine, 2,6-di-tert-butylphenylhydrazine,2-phenylphenylhydrazine, 4-phenylphenylhydrazine,2,4-diphenylphenylhydrazine, 2,6-diphenylphenylhydrazine,pentafluorophenylhydrazine, 3,5-bis(trifluoromethyl)phenylhydrazine,naphthylhydrazine and the like; and aliphatic hydrazines such asmethylhydrazine, ethylhydrazine, isopropylhydrazine,tert-butylhydrazine, n-butylhydrazine, isobutylhydrazine,n-pentylhydrazine, n-hexylhydrazine, cyclohexylhydrazine,n-decylhydrazine, benzylhydrazine and the like. The amount of hydrazineto be used is usually about 0.5 to 1.5 moles relative to 1 mole of thecarbonyl compound.

The above reaction is usually carried out in a solvent. Such a solventincludes, for example, alcohol solvents such as methanol, ethanol,isopropanol and the like; aprotic solvents such as aromatic hydrocarbonsolvents such as benzene, toluene and the like; aliphatic hydrocarbonsolvents such as hexane, heptane and the like; ether solvents such asdiethyl ether, tetrahydrofuran, 1,4-dioxane and the like; amide solventssuch as hexamethylphosphoric amide, dimethylformamide and the like;polar solvents such as acetonitrile, propionitrile, acetone, diethylketone, methyl isobutyl ketone, cyclohexanone and the like; halogenatedsolvents such as dichloromethane, dichloroethane, chlorobenzene,dichlorobenzene and the like. One or a mixture of two or more of thesolvents is used. The amount of a solvent to be used is usually in therange of 1 to 200 parts by weight, preferably 3 to 50 parts by weightrelative to 1 part by weight of the carbonyl compound of the formula(1).

The reaction temperature is usually in the range of −100° C. to theboiling point of a solvent, preferably −80 to 120° C.

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer can not beeasily separated due to use of a solvent compatible with water or use ofa small amount of solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate or chlorobenzene to the reaction mixture. Thehydrazone compound represented by the formula (7) can be purified, forexample, by washing said solution of the compound with water, dryingsaid solution, and then distilling off the solvent, and further bymethods such as recrystallization, distillation, column chromatographytreatment and the like.

Specific examples of the hydrazone compound represented by the formula(7) include the following compound:

2-(cyclopentadienyl)benzaldehyde phenylhydrazone,2-(2-methylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(3-methylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2-tert-butylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(3-tert-butylcyclopentadienyl)benzaldehyde phenylhydrazone,2-(2-dimethylaminocyclopentadienyl)benzaldehyde phenylhydrazone,2-(3-dimethylaminocyclopentadienyl)benzaldehyde phenylhydrazone,2-(inden-1-yl)benzaldehyde phenylhydrazone,2-(2-methylinden-1-yl)benzaldehyde phenylhydrazone,2-(2-phenylinden-1-yl)benzaldehyde phenylhydrazone,2-(fluoren-1-yl)benzaldehyde phenylhydrazone,2-(cyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2-methylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(3-methylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde 2-methylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde2-methylphenylhydrazone, 2-(2-tert-butylcyclopentadienyl)benzaldehyde2-methylphenylhydrazone, 2-(3-tert-butylcyclopentadienyl)benzaldehyde2-methylphenylhydrazone, 2-(2-dimethylaminocyclopentadienyl)benzaldehyde2-methylphenylhydrazone, 2-(3-dimethylaminocyclopentadienyl)benzaldehyde2-methylphenylhydrazone, 2-(inden-1-yl)benzaldehyde2-methylphenylhydrazone, 2-(2-methylinden-1-yl)benzaldehyde2-methylphenylhydrazone, 2-(2-phenylinden-1-yl)benzaldehyde2-methylphenylhydrazone, 2-(fluoren-1-yl)benzaldehyde2-methylphenylhydrazone, 2-(cyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(2-methylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(3-methylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2-tert-butylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(3-tert-butylcyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(2-dimethylaminocyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone,2-(3-dimethylaminocyclopentadienyl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(inden-1-yl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(2-methylinden-1-yl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(2-phenylinden-1-yl)benzaldehyde2,4,6-trimethylphenylhydrazone, 2-(fluoren-1-yl)benzaldehyde2,4,6-trimethylphenylhydradzone, 2-(cyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(2-methylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(3-methylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2-tert-butylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(3-tert-butylcyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(2-dimethylaminocyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone,2-(3-dimethylaminocyclopentadienyl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(inden-1-yl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(2-methylinden-1-yl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(2-phenylinden-1-yl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(fluoren-1-yl)benzaldehyde2,6-diisopropylphenylhydrazone, 2-(cyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2-methylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(3-methylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2,3-dimethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2,4-dimethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(3,4-dimethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2-tert-butylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(3-tert-butylcyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(2-dimethylaminocyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(3-dimethylaminocyclopentadienyl)benzaldehyde2-naphthylhydrazone, 2-(inden-1-yl)benzaldehyde 2-naphthylhydrazone,2-(2-methylinden-1-yl)benzaldehyde 2-naphthylhydrazone,2-(2-phenylinden-1-yl)benzaldehyde 2-naphthylhydrazone,2-(fluoren-1-yl)benzaldehyde 2-naphthylhydrazone,2-(cyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2-methylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(3-methylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde-cyclohexylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2-tert-butylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(3-tert-butylcyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(2-dimethylaminocyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(3-dimethylaminocyclopentadienyl)benzaldehyde cyclohexylhydrazone,2-(inden-1-yl)benzaldehyde cyclohexylhydrazone,2-(2-methylinden-1-yl)benzaldehyde cyclohexylhydrazone,2-(2-phenylinden-1-yl)benzaldehyde cyclohexylhydrazone,2-(fluoren-1-yl)benzaldehyde cyclohexylhydrazone,2-(cyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2-methylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(3-dimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2,3-dimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2,4-dimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(3,4-dimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2-tert-butylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(3-tert-butylcyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(2-dimethylaminocyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(3-dimethylaminocyclopentadienyl)benzaldehyde tert-butylhydrazone,2-(inden-1-yl)benzaldehyde tert-butylhydrazone,2-(2-methylinden-1-yl)benzaldehyde tert-butylhydrazone,2-(2-phenylinden-1-yl)benzaldehyde tert-butylhydrazone,2-(fluoren-1-yl)benzaldehyde tert-butylhydrazone,2-(cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2-methylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(3-methylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2,3-dimethylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2,4-dimethylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(3,4-dimethylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)-1-naphthaldehyde phenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthaldehydephenylhydrazone, 2-(2-tert-butylcyclopentadienyl)-1-naphthaldehydephenylhydrazone, 2-(3-tert-butylcyclopentadienyl)-1-naphthaldehydephenylhydrazone, 2-(2-dimethylaminocyclopentadienyl)-1-naphthaldehydephenylhydrazone, 2-(3-dimethylaminocyclopentadienyl)-1-naphthaldehydephenylhydrazone, 2-(inden-1-yl)-1-naphthaldehyde phenylhydrazone,2-(2-methylinden-1-yl)-1-naphthaldehyde phenylhydrazone,2-(2-phenylinden-1-yl)-1-naphthaldehyde phenylhydrazone,2-(fluoren-1-yl)-1-naphthaldehyde phenylhydrazone,2-(cyclopentadienyl)acetophenone phenylhydrazone,2-(2-methylcyclopentadienyl)acetophenone phenylhydrazone,2-(3-methylcyclopentadienyl)acetophenone phenylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone phenylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone phenylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone phenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone phenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone phenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone phenylhydrazone,2-(2-tert-butylcyclopentadienyl)acetophenone phenylhydrazone,2-(3-tert-butylcyclopentadienyl)acetophenone phenylhydrazone,2-(2-dimethylaminocyclopentadienyl)acetophenone phenylhydrazone,2-(3-dimethylaminocyclopentadienyl)acetophenone phenylhydrazone,2-(inden-1-yl)acetophenone phenylhydrazone,2-(2-methylinden-1-yl)acetophenone phenylhydrazone,2-(2-phenylinden-1-yl)acetophenone phenylhydrazone,2-(fluoren-1-yl)acetophenone phenylhydrazone,2-(cyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(2-methylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(3-methylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone 2-methylphenylhydrazone;2-(2,4,5-trimethylcyclopentadienyl)acetophenone 2-methylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone2-methylphenylhydrazone, 2-(2-tert-butylcyclopentadienyl)acetophenone2-methylphenylhydrazone, 2-(3-tert-butylcyclopentadienyl)acetophenone2-methylphenylhydrazone, 2-(2-dimethylaminocyclopentadienyl)acetophenone2-methylphenylhydrazone, 2-(3-dimethylaminocyclopentadienyl)acetophenone2-methylphenylhydrazone, 2-(inden-1-yl)acetophenone2-methylphenylhydrazone, 2-(2-methylinden-1-yl)acetophenone2-methylphenylhydrazone, 2-(2-phenylinden-1-yl)acetophenone2-methylphenylhydrazone, 2-(fluoren-1-yl)acetophenone2-methylphenylhydrazone, 2-(cyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(2-methylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(3-methylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2-tert-butylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(3-tert-butylcyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(2-dimethylaminocyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone,2-(3-dimethylaminocyclopentadienyl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(inden-1-yl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(2-methylinden-1-yl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(2-phenylinden-1-yl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(fluoren-1-yl)acetophenone2,4,6-trimethylphenylhydrazone, 2-(cyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone, 2-(2-methylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone, 2-(3-methylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2-tert-butylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(3-tert-butylcyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(2-dimethylaminocyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone,2-(3-dimethylaminocyclopentadienyl)acetophenone2,6-diisopropylphenylhydrazone, 2-(inden-1-yl)acetophenone2,6-diisopropylphenylhydrazone, 2-(2-methylinden-1-yl)acetophenone2,6-diisopropylphenylhydrazone, 2-(2-phenylinden-1-yl)acetophenone2,6-diisopropylphenylhydrazone, 2-(fluoren-1-yl)acetophenone2,6-diisopropylphenylhydrazone, 2-(cyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2-methylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(3-methylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2,3-dimethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2,4-dimethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(3,4-dimethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2,3,4-trimethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2,4,5-trimethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2-tert-butylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(3-tert-butylcyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(2-dimethylaminocyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(3-dimethylaminocyclopentadienyl)acetophenone2-naphthylhydrazone, 2-(inden-1-yl)acetophenone 2-naphthylhydrazone,2-(2-methylinden-1-yl)acetophenone 2-naphthylhydrazone,2-(2-phenylinden-1-yl)acetophenone 2-naphthylhydrazone,2-(fluoren-1-yl)acetophenone 2-naphthylhydrazone,2-(cyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2-methylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(3-methylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2-tert-butylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(3-tert-butylcyclopentadienyl)acetophenone cyclohexylhydrazone,2-(2-dimethylaminocyclopentadienyl)acetophenone cyclohexylhydrazone,2-(3-dimethylaminocyclopentadienyl)acetophenone cyclohexylhydrazone,2-(inden-1-yl)acetophenone cyclohexylhydrazone,2-(2-methylinden-1-yl)acetophenone cyclohexylhydrazone,2-(2-phenylinden-1-yl)acetophenone cyclohexylhydrazone,2-(fluoren-1-yl)acetophenone cyclohexylhydrazone,2-(cyclopentadienyl)acetophenone tert-butylhydrazone,2-(2-methylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(3-methylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2,3-dimethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2,4-dimethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(3,4-dimethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2-tert-butylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(3-tert-butylcyclopentadienyl)acetophenone tert-butylhydrazone,2-(2-dimethylaminocyclopentadienyl)acetophenone tert-butylhydrazone,2-(3-dimethylaminocyclopentadienyl)acetophenone tert-butylhydrazone,2-(inden-1-yl)acetophenone tert-butylhydrazone,2-(2-methylinden-1-yl)acetophenone tert-butylhydrazone,2-(2-phenylinden-1-yl)acetophenone tert-butylhydrazone,2-(fluoren-1-yl)acetophenone tert-butylhydrazone and the like.

The substituted cyclopentadiene compound represented by the formula (8):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the same meanings asdefined in the formula (I), is hereinafter explained.

The compound of the formula (8) can be produced by reacting a nitrilecompound represented by the formula (10):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the same meanings asdefined in the formula (II), or a compound represented by the formula(11):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R³⁰ have the samemeanings as defined in the formula (II), with a nucleophilic agent (anorganic lithium compound or an organic magnesium compound).

A nucleophilic agent used in the reaction includes the above-mentionedorganic lithium compounds or organic magnesium compounds and the like(R¹Li or R¹MgX; wherein X is a halogen atom; provided that R¹ is not ahydrogen atom).

Such a nucleophilic agent includes methylmagnesium bromide,ethylmagnesium bromide, phenylmagnesium bromide, n-butylmagnesiumbromide, t-butylmagnesium bromide, methyllithium, phenyllithium,t-butyllithium and the like. Similarly, the above-mentioned compounds inwhich magnesium bromide is changed to magnesium chloride or magnesiumiodide are also exemplified.

Although 2-(4-methoxy-inden-1-yl)benzonitrile (Bioorg. Med. Chem. Lett.,1993, 3, 55) has been known to be obtained by reactingmethylchloroaluminum amide, which is derived from hard-to-handletrimethylaluminum, with the precursor spirolactone, said method is notnecessarily a general synthesis method and is not satisfactory becauseamide and carboxylic acid are simultaneously produced as by-products.However, according to the method of the present invention, the nitrilecompound of the present invention including the above-mentioned nitrilecompound can be easily obtained.

Specific examples of the nitrile compound represented by the formula(10) include the following compounds:

2-(cyclopentadienyl)benzonitrile,2-(2-methylcyclopentadienyl)benzonitrile,2-(3-methylcyclopentadienyl)benzonitrile,2-(2,3-dimethylcyclopentadienyl)benzonitrile,2-(2,4-dimethylcyclopentadienyl)benzonitrile,2-(2,3,4-trimethylcyclopentadienyl)benzonitrile,2-(2,3,5-trimethylcyclopentadienyl)benzonitrile,2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile,2-(2-dimethylaminocyclopentadienyl)benzonitrile,2-(3-dimethylaminocyclopentadienyl)benzonitrile,2-(inden-1-yl)benzonitrile, 2-(2-methylinden-1-yl)benzonitrile,2-(2-phenylinden-1-yl)benzonitrile,2-(cyclopentadienyl)-1-cyanonaphthalene,2-(2-methylcyclopentadienyl)-1-cyanonaphthalene,2-(3-methylcyclopentadienyl)-1-cyanonaphthalene,2-(2,3-dimethylcyclopentadienyl)-1-cyanonaphthalene,2-(2,4-dimethylcyclopentadienyl)-1-cyanonaphthalene,2-(2,3,4-trimethylcyclopentadienyl)-1-cyanonaphthalene,2-(2,3,5-trimethylcyclopentadienyl)-1-cyanonaphthalene,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-cyanonaphthalene,2-(2-dimethylaminocyclopentadienyl)-1-cyanonaphthalene,2-(3-dimethylaminocyclopentadienyl)-1-cyanonaphthalene,2-(inden-1-yl)-1-cyanonaphthalene,2-(2-methylinden-1-yl)-1-cyanonaphthalene,2-(2-phenylinden-1-yl)-1-cyanonaphthalene,3-(cyclopentadienyl)-2-cyanonaphthalene,3-(2-methylcyclopentadienyl)-2-cyanonaphthalene,3-(3-methylcyclopentadienyl)-2-cyanonaphthalene,3-(2,3-dimethylcyclopentadienyl)-2-cyanonaphthalene,3-(2,4-dimethylcyclopentadienyl)-2-cyanonaphthalene,3-(2,3,4-trimethylcyclopentadienyl)-2-cyanonaphthalene,3-(2,3,5-trimethylcyclopentadienyl)-2-cyanonaphthalene,3-(2,3,4,5-tetramethylcyclopentadienyl)-2-cyanonaphthalene,3-(2-dimethylaminocyclopentadienyl)-2-cyanonaphthalene,3-(3-dimethylaminocyclopentadienyl)-2-cyanonaphthalene,3-(inden-1-yl)-2-cyanonaphthalene,3-(2-methylinden-1-yl)-2-cyanonaphthalene,3-(2-phenylinden-1-yl)-2-cyanonaphthalene,3-dimethylamino-6-(cyclopentadienyl)benzonitrile,3-dimethylamino-6-(2-methylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(3-methylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile,3-dimethylamino-6-(2-dimethylaminocyclopentadienyl)benzonitrile,3-dimethylamino-6-(3-dimethylaminocyclopentadienyl)benzonitrile,3-dimethylamino-6-(inden-1-yl)benzonitrile,3-dimethylamino-6-(2-methylinden-1-yl)benzonitrile,3-dimethylamino-6-(2-phenylinden-1-yl)benzonitrile and the like.

Specific examples of the oxime ether compound represented by the formula(11) include the following compounds:

O-Methyl-2-(cyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2-methylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(3-methylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2,3-dimethylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2,4-dimethylcyclopentadienyl)benzaldehyde oxime,o-methyl-2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde oxime,O-methyl-2-(2-dimethylaminocyclopentadienyl)benzaldehyde oxime,O-methyl-2-(3-dimethylaminocyclopentadienyl)benzaldehyde oxime,O-methyl-2-(inden-1-yl)benzaldehyde oxime,O-methyl-2-(2-methylinden-1-yl)benzaldehyde oxime,O-methyl-2-(2-phenylinden-1-yl)benzaldehyde oxime,O-methyl-2-(cyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2-methylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-(3-methylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2,3-dimethylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2,4-dimethylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2,3,4-trimethylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2,3,5-trimethylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(2-dimethylaminocyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(3-dimethylaminocyclopentadienyl)-1-naphthaldehyde oxime,O-methyl-2-(inden-1-yl)-1-naphthaldehyde oxime,O-methyl-2-(2-methylinden-1-yl)-1-naphthaldehyde oxime,O-methyl-2-(2-phenylinden-1-yl)-1-naphthaldehyde oxime,O-methyl-3-(cyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2-methylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(3-methylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2,3-dimethylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2,4-dimethylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2,3,4-trimethylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2,3,4,5-trimethylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2,3,4,5-tetramethylcyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(2-dimethylaminocyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(3-dimethylaminocyclopentadienyl)-2-naphtaldehyde oxime,O-methyl-3-(inden-1-yl)-2-naphtaldehyde oxime,O-methyl-3-(2-methylinden-1-yl)-2-naphtaldehyde oxime,O-methyl-3-(2-phenylinden-1-yl)-2-naphtaldehyde oxime,O-methyl-3-dimethylamino-6-(cyclopentadienyl)benzaldehyde oxime,O-methyl-3-dimethylamino-6-(2-methylcyclopentadienyl)benzaldehyde oxime,O-methyl-3-dimethylamino-6-(3-methylcyclopentadienyl)benzaldehyde oxime,O-methyl-3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(2-dimethylaminocyclopentadienyl)benzaldehydeoxime,O-methyl-3-dimethylamino-6-(3-dimethylaminocyclopentadienyl)benzaldehyde-oxime,O-methyl-3-dimethylamino-6-(inden-1-yl)benzaldehyde oxime,O-methyl-3-dimethylamino-6-(2-methylinden-1-yl)benzaldehyde oxime,O-methyl-3-dimethylamino-6-(2-phenylinden-1-yl)benzaldehyde oxime andthe like. Similarly, the above-mentioned compounds in which O-methyl ischanged to O-ethyl or O-benzyl are also exemplified.

There are isomers based on the nitrogen-oxygen bond of oxime ether. Thepresent invention also encompasses the isomers and a mixture thereof.

The reaction of a nucleophilic agent and the compound of the formula(10) or (11) is usually carried out in an inert solvent to the reaction.Such a solvent includes, for example, aprotic solvents such as aromatichydrocarbon solvents such as benzene, toluene and the like; aliphatichydrocarbon solvents such as hexane, heptane and the like; ethersolvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and thelike; amide solvents such as hexamethylphosphoric amide,dimethylformamide and the like; polar solvents such as acetonitrile,propionitrile, acetone, diethyl ketone, methyl isobutyl ketone,cyclohexanone and the like; halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene and thelike. One or a mixture of two or more of the solvents is used. Theamount of a solvent to be used is usually in the range of 1 to 200times, preferably 3 to 50 times the weight of the substitutedcyclopentadiene of the formula (10) or (11).

The reaction temperature is usually in the range of −100° C. to theboiling point of a solvent, preferably −80 to 120° C.

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer can not beeasily separated due to use of a solvent compatible with water or use ofa small amount of solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate, chlorobenzene and the like to the reactionmixture. The imine compound represented by the formula (8) can bepurified, for example, by washing said solution of the compound withwater, drying said solution, and then distilling off the solvent, andfurther by methods such as recrystallization, distillation, columnchromatography treatment and the like.

Specific examples of the imine compound of the formula (8) thus obtainedinclude the following compounds:

2-(cyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(3-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,2-(inden-1-yl)-α-tert-butyl-benzenemethanimine,2-(2-methylinden-1-yl)-α-tert-butyl-benzenemethanimine,2-(2-phenylinden-1-yl)-α-tert-butyl-benzenemethanimine,2-(fluoren-1-yl)-α-tert-butyl-benzenemethanimine,2-(cyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2-methylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(3-methylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,2-(inden-1-yl)-α-n-butyl-benzenemethanimine,2-(2-methylinden-1-yl)-α-n-butyl-benzenemethanimine,2-(2-phenylinden-1-yl)-α-n-butyl-benzenemethanimine,2-(fluoren-1-yl)-α-n-butyl-benzenemethanimine,2-(cyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2-methylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(3-methylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimine,2-(inden-1-yl)-α-phenyl-benzenemethanimine,2-(2-methylinden-1-yl)-α-phenyl-benzenemethanimine,2-(2-phenylinden-1-yl)-α-phenyl-benzenemethanimine,2-(fluoren-1-yl)-α-phenyl-benzenemethanimine,2-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,2-(cyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(3-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl-α-cyclohexyl-benzenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,2-(inden-1-yl)-α-cyclohexyl-benzenemethanimine,2-(2-methylinden-1-yl)-α-cyclohexyl-benzenemethanimine,2-(2-phenylinden-1-yl)-α-cyclohexyl-benzenemethanimine,2-(fluoren-1-yl)-α-cyclohexyl-benzenemethanimine,2-(cyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2-methylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(3-methylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-1-naphthalenemethanimine,2-(inden-1-yl)-α-tert-butyl-1-naphthalenemethanimine,2-(2-methylinden-1-yl)-α-tert-butyl-1-naphthalenemethanimine,2-(2-phenylinden-1-yl)-α-tert-butyl-1-naphthalenemethanimine,2-(fluoren-1-yl)-α-tert-butyl-1-naphthalenemethanimine,2-(cyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2-methylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(3-methylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-1-naphthalenemethanimine,2-(inden-1-yl)-α-n-butyl-1-naphthalenemethanimine,2-(2-methylinden-1-yl)-α-n-butyl-1-naphthalenemethanimine,2-(2-phenylinden-1-yl)-α-n-butyl-1-naphthalenemethanimine,2-(fluoren-1-yl)-α-n-butyl-1-naphthalenemethanimine,2-(cyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2-methylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(3-methylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-1-naphthalenemethanimine,2-(inden-1-yl)-α-phenyl-1-naphthalenemethanimine,2-(2-methylinden-1-yl)-α-phenyl-1-naphthalenemethanimine,2-(2-phenylinden-1-yl)-α-phenyl-1-naphthalenemethanimine,2-(fluoren-1-yl)-α-phenyl-1-naphthalenemethanimine,2-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-1-naphthalenemethanimine,2-(cyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2-methylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(3-methylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-1-naphthalenemethanimine,2-(inden-1-yl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2-methylinden-1-yl)-α-cyclohexyl-1-naphthalenemethanimine,2-(2-phenylinden-1-yl)-α-cyclohexyl-1-naphthalenemethanimine,2-(fluoren-1-yl)-α-cyclohexyl-1-naphthalenemethanimine,3-(cyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2-methylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(3-methylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine;3-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-2-naphthalenemethanimine,3-(inden-1-yl)-α-tert-butyl-2-naphthalenemethanimine,3-(2-methylinden-1-yl)-α-tert-butyl-2-naphthalenemethanimine,3-(2-phenylinden-1-yl)-α-tert-butyl-2-naphthalenemethanimine,3-(fluoren-1-yl)-α-tert-butyl-2-naphthalenemethanimine,3-(cyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2-methylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(3-methylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2,3-dimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2,4-dimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-2-5-naphthalenemethanimine,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-2-naphthalenemethanimine,3-(inden-1-yl)-α-n-butyl-2-naphthalenemethanimine,3-(2-methylinden-1-yl)-α-n-butyl-2-naphthalenemethanimine,3-(2-phenylinden-1-yl)-α-n-butyl-2-naphthalenemethanimine,3-(fluoren-1-yl)-α-n-butyl-2-naphthalenemethanimine,3-(cyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2-methylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(3-methylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2,3-dimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2,4-dimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-2-naphthalenemethanimine,3-(inden-1-yl)-α-phenyl-2-naphthalenemethanimine,3-(2-methylinden-1-yl)-α-phenyl-2-naphthalenemethanimine,3-(2-phenylinden-1-yl)-α-phenyl-2-naphthalenemethanimine,3-(fluoren-1-yl)-α-phenyl-2-naphthalenemethanimine,3-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-2-naphthalenemethanimine,3-(cyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2-methylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(3-methylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-2-naphthalenemethanimine,3-(inden-1-yl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2-methylinden-1-yl)-α-cyclohexyl-2-naphthalenemethanimine,3-(2-phenylinden-1-yl)-α-cyclohexyl-2-naphthalenemethanimine,3-(fluoren-1-yl)-α-cyclohexyl-2-naphthalenemethanimine,3-dimethylamino-6-(cyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(inden-1-yl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2-methylinden-1-yl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(2-phenylinden-1-yl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(fluoren-1-yl)-α-tert-butyl-benzenemethanimine,3-dimethylamino-6-(cyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(inden-1-yl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2-methylinden-1-yl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(2-phenylinden-1-yl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(fluoren-1-yl)-α-n-butyl-benzenemethanimine,3-dimethylamino-6-(cyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(inden-1-yl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2-methylinden-1-yl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(2-phenylinden-1-yl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(fluoren-1-yl)-α-phenyl-benzenemethanimine,3-dimethylamino-6-(cyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(inden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2-methylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(2-phenylinden-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(fluoren-1-yl)-α-(2,3,4-trimethylphenyl)-benzenemethanimine,3-dimethylamino-6-(cyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(3-methylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2,3-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2,4-dimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2,3,4-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2,3,5-trimethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2,3,4,5-tetramethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(3-dimethylaminomethylcyclopentadienyl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(inden-1-yl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2-methylinden-1-yl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(2-phenylinden-1-yl)-α-cyclohexyl-benzenemethanimine,3-dimethylamino-6-(fluoren-1-yl)-α-cyclohexyl-benzenemethanimine and thelike.

The nitrile compound of the formula (10) can be produced by reacting theoxime ether compound of formula (11) with a base.

A base to be reacted with the compound of the formula (11) includesmethyllithium, ethyllithium, n-butyllithium, sec-butyllithium, lithiumtrimethylsilyl acetylide, trimethylsilylmethyllithium, vinyllithium,phenyllithium, lithium methoxide, lithium ethoxide, lithiumtert-butoxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide,potassium methoxide, potassium ethoxide, potassium tert-butoxide,lithium amide, lithium dimethylamide, lithium diisopropylamide, lithiumbis(trimethylsilyl)amide, sodium amide, sodium diisopropylamide, sodiumbis(trimethylsilyl)amide and the like, preferably alkali metal amidessuch as lithium amide, lithium dimethylamide, lithium diisopropylamide,lithium bis(trimethylsilyl)amide, sodium amide, sodium diisopropylamide,sodium bis(trimethylsilyl)amide and the like.

The amount of a base to be used is usually in the range of about 0.5 to3 moles, preferably about 1.9 to 2.5 moles relative to 1 mole of theoxime ether compound represented by the formula (11).

A method for the reaction is not specifically limited, but usually themethod can comprise addition in dropwise of a base to the oxime ethercompound represented by the formula (11) in the presence of a solvent oraddition of the oxime ether compound represented by the formula (11) toa base. The reaction temperature is usually from −80° C. to the boilingpoint of a solvent, preferably −80 to 40° C.

A solvent used in the reaction is an inert solvent to the reaction. Sucha solvent includes aromatic hydrocarbon solvents such as benzene,toluene, xylene and the like; aliphatic hydrocarbon solvents such ashexane, heptane and the like; ether solvents such as diethyl ether,tetrahydrofuran, 1,4-dioxane and the like; amide solvents such ashexamethylphosphoric triamide, dimethylformamide and the like. One or amixture of two or more of the solvents is used. The amount of a solventto be used is usually in the range of 1 to 200 parts by weight,preferably 3 to 50 parts by weight relative to 1 part by weight of theoxime ether compound represented by the formula (11).

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer can not beeasily separated due to use of a solvent compatible with water or use ofa small amount of solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate, chlorobenzene and the like to the reactionmixture.

In order to isolate the nitrile compound represented by the formula(10), for example, by washing said solution of the compound with water,drying said solution, and then distilling off the solvent, and furtherby methods such as recrystallization, distillation, columnchromatography treatment and the like.

The oxime ether compound of the formula (11) can be produced by reactingthe carbonyl compound of the formula (1) with oxime ether according to aconventional method.

By reacting the substituted cyclopentadiene ligand compound of theformula (II) thus obtained with the transition metal compound of theformula (III), the transition metal complex of the formula (I) can beproduced.

The X¹ to X⁴ for the transition metal compound of the formula (III) arealready explained. Said transition metal compound in which each of X¹ toX⁴ is a C₁₋₅ hydrocarbon-substituted amino group is preferably used forthe production of the transition metal complex.

The transition metal compound represented by the formula (III) includestetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium,tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium,tetrakis(dimethylamino)hafnium, tetrakis(diethylamino)hafnium,tris(dimethylamino)titanium chloride, tris(diethylamino)titaniumchloride, tris(dimethylamino)zirconium chloride,tris(diethylamino)zirconium chloride, tris(dimethylamino)hafniumchloride, tris(diethylamino)hafnium chloride, bis(dimethylamino)titaniumdichloride, bis(diethylamino)titanium dichloride,bis(dimethylamino)zirconium dichloride, bis(diethylamino)zirconiumdichloride, bis(dimethylamino)hafnium dichloride,bis(diethylamino)hafnium dichloride and the like.

The above reaction is usually carried out in an inert solvent to thereaction. Such a solvent includes, for example, aprotic solvents such asaromatic hydrocarbon solvents such as benzene, toluene and the like;aliphatic hydrocarbon solvents such as hexane, heptane and the like;ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane andthe like; amide solvents such as hexamethylphosphoric amide,dimethylformamide and the like; polar solvents such as acetonitrile,propionitrile, acetone, diethyl ketone, methyl isobutyl ketone,cyclohexanone and the like; halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene and thelike, preferably aromatic hydrocarbon solvents such as benzene, tolueneand the like; aliphatic hydrocarbon solvents such as hexane, heptane andthe like. One or a mixture of two or more of the solvents is used. Theamount of a solvent to be used is usually in the range of 1 to 200 partsby weight, preferably 3 to 50 parts by weight relative to 1 part byweight of the substituted cyclopentadiene ligand compound represented bythe formula (II).

This reaction can be usually carried out by adding the substitutedcyclopentadiene represented by the formula (II) to a solvent and thenadding the transition metal compound represented by the formula (III)thereto. Thus the transition metal complex represented by the formula(I) can be obtained.

The reaction temperature is usually in the range of −100° C. to theboiling point of a solvent, preferably −80 to 120° C.

The transition metal complex wherein X¹ and X² are each a substitutedamino group is converted to a halide thereof by reacting with a halogencompound such as a chlorosilane compound or a hydrogen chloride. Thetransition metal complex thus obtained includes the compounds describedin the explanation for the formulas (I-1), (I-2), (I-3) and (I-4).

Hereinafter the carbonyl compound of formula (I), which is a startingmaterial for the substituted cyclopentadiene ligand compounds (5), (6),(7) and (8), and a production method thereof are explained.

The carbonyl compound of the formula (I) is produced by reacting thehalogen compound of formula (2) and the cyclopentenone of the formula(3) in the presence of a magnesium compound or an organic lithiumcompound and then treating the resultant cyclopentenol represented bythe formula (4) with an acid.

In the halogen compound represented by the formula (2), the substituentX represents a chlorine, bromine or iodine atom, preferably a bromineatom or an iodine atom.

The optionally substituted C₁₋₁₀ alkyl group for the substituents R¹⁰and R¹¹ includes a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, an-octyl group, a n-decyl group, a fluoromethyl group, a difluoromethylgroup, a trifluoromethyl group, a fluoroethyl group, a difluoroethylgroup, a trifluoroethyl group, a tetrafluoroethyl group, apentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group,a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group,a perfluorodecyl group and the like, and preferably a methyl group, anethyl group, an isopropyl group, a tert-butyl group, an amyl group andthe like are exemplified. Alternatively, R¹⁰ and R¹¹ may be linked toeach other to form a 5- or 6-membered ring, and preferably an ethylenegroup and a propylene group are exemplified.

Specific examples of such a halogen compound include1-chloro-2-(1,3-dioxolan-2-yl)-benzene,1-chloro-2-(2-methyl-1,3-dioxolan-oxolan-2-yl)-benzene,1-chloro-2-(2-ethyl-1,3-oxolan-2-yl)-benzene,1-chloro-2-(2-phenyl-1,3-oxolan-2-yl)-benzene,1-chloro-2-(dimethoxymethyl)-benzene,1-chloro-2-(1,1-dimethoxyethyl)-benzene,1-chloro-2-(1,1-dimethoxy-1-phenylmethyl)-benzene,1-bromo-2-(1,3-dioxolan-2-yl)-benzene,1-bromo-2-(2-methyl-1,3-dioxolan-2-yl)-benzene,1-bromo-2-(2-ethyl-1,3-dioxolan-2-yl)-benzene,1-bromo-2-(2-phenyl-1,3-dioxolan-2-yl)-benzene,1-bromo-2-(dimethoxymethyl)-benzene,1-bromo-2-(1,1-dimethoxyethyl)-benzene,1-bromo-2-(1,1-dimethoxy-1-phenylmethyl)-benzene,1-iodo-2-(1,3-dioxolan-2-yl)-benzene,1-iodo-2-(2-methyl-1,3-dioxolan-2-yl)-benzene,1-iodo-2-(2-ethyl-1,3-dioxolan-2-yl)-benzene,1-iodo-2-(2-phenyl-1,3-dioxolan-2-yl)-benzene,1-iodo-2-(dimethoxymethyl)-benzene,1-iodo-2-(1,1-dimethoxyethyl)-benzene,1-iodo-2-(1,1-dimethoxy-1-phenylmethyl)-benzene,1-chloro-2-(1,3-dioxolan-2-yl)-naphthalene,1-chloro-2-(2-methyl-1,3-dioxolan-2-yl)-naphthalene,1-chloro-2-(2-ethyl-1,3-dioxolan-2-yl)-naphthalene,1-chloro-2-(2-phenyl-1,3-dioxolan-2-yl)-naphthalene,1-chloro-2-(dimethoxymethyl)-naphthalene,1-chloro-2-(1,1-dimethoxyethyl)-naphthalene,1-chloro-2-(1,1-dimethoxy-1-phenylmethyl)-naphthalene,1-bromo-2-(1,3-dioxolan-2-yl)-naphthalene,1-bromo-2-(2-methyl-1,3-dioxolan-2-yl)-naphthalene,1-bromo-2-(2-ethyl-1,3-dioxolan-2-yl)-naphthalene,1-bromo-2-(2-phenyl-1,3-dioxolan-2-yl)-naphthalene,1-bromo-2-(dimethoxymethyl)-naphthalene,1-bromo-2-(1,1-dimethoxyethyl)-naphthalene,1-bromo-2-(1,1-dimethoxy-1-phenylmethyl)-naphthalene,1-iodo-2-(1,3-dioxolan-2-yl)-naphthalene,1-iodo-2-(2-methyl-1,3-dioxolan-2-yl)-naphthalene,1-iodo-2-(2-ethyl-1,3-dioxolan-2-yl)-naphthalene,1-iodo-2-(2-phenyl-1,3-dioxolan-2-yl)-naphthalene,1-iodo-2-(dimethoxymethyl)-naphthalene,1-iodo-2-(1,1-dimethoxyethyl)-naphthalene,1-iodo-2-(1,1-dimethoxy-1-phenylmethyl)-naphthalene,1-chloro-2-(1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-chloro-2-(2-methyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-chloro-2-(2-ethyl-1,3-oxolan-2-yl)-4-tert-butylbenzene,1-chloro-2-(2-phenyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-chloro-2-(dimethoxymethyl)-4-tert-butylbenzene,1-chloro-2-(1,1-dimethoxyethyl)-4-tert-butylbenzene,1-chloro-2-(1,1-dimethoxy-1-phenylmethyl)-4-tert-butylbenzene,1-bromo-2-(1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-bromo-2-(2-methyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-bromo-2-(2-ethyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-bromo-2-(2-phenyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-bromo-2-(dimethoxymethyl)-4-tert-butylbenzene,1-bromo-2-(1,1-dimethoxyethyl)-4-tert-butylbenzene,1-bromo-2-(1,1-dimethoxy-1-phenylmethyl)-4-tert-butylbenzene,1-iodo-2-(1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-iodo-2-(2-methyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-iodo-2-(2-ethyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-iodo-2-(2-phenyl-1,3-dioxolan-2-yl)-4-tert-butylbenzene,1-iodo-2-(dimethoxymethyl)-4-tert-butylbenzene,1-iodo-2-(1,1-dimethoxyethyl)-4-tert-butylbenzene,1-iodo-2-(1,1-dimethoxy-1-phenylmethyl)-4-tert-butylbenzene and thelike.

The first step of production process of the carbonyl compound of theformula (1) is a step of reacting the halogen compound represented bythe formula (2) and the cyclopentenone represented by the formula (3) inthe presence of a magnesium compound or an organic lithium compound togive the cyclopentenol represented by the formula (4).

An organic lithium compound used in the above reaction includesmethyllithium, ethyllithium, n-butyllithium, sec-butyllithium,tert-butyllithium, phenyllithium and the like. The amount of an organiclithium compound to be used is usually in the range of 0.5 to 3 moles,preferably 0.9 to 2.5 moles relative to 1 mole of the halogen compoundrepresented by the formula (2).

The cyclopentenone represented by the formula (3) includes2-cyclopentenone, 2-methylcyclopentenone, 3-methylcyclopentenone,2,3-dimethylcyclopentenone, 2,4-dimethylcyclopentenone,3,4-dimethylcyclopentenone, 2,3,4-trimethylcyclopentenone,2,3,5-trimethylcyclopentenone, 2,3,4,5-tetramethylcyclopentenone,2-tert-butylcyclopentenone, 3-tert-butylcyclopentenone,4-tert-butylcyclopentenone, 5-tert-butylcyclopentenone,2-dimethylaminocyclopentenone, 3-dimethylaminocyclopentenone,4-dimethylaminocyclopentenone, 5-dimethylaminocyclopentenone,2-methylindanone, 2-phenylindanone, 2-trimethylsilylcyclopentenone,3-trimethylsilylcyclopentenone, 4-trimethylsilylcyclopentenone, and5-trimethylsilylcyclopentenone.

The above reaction is usually carried out by reacting the halogencompound represented by the formula (2) with a magnesium compound or anorganic lithium compound in the presence of a solvent and then addingthe cyclopentenone represented by the formula (3) thereto. Thetemperature for reacting the halogen compound represented by the formula(2) with a magnesium compound or an organic lithium compound is usuallyfrom −80° C. to the boiling point of a solvent. When the halogencompound represented by the formula (2) is reacted with an organiclithium compound, the range of −80 to 40° C. is preferred, and when usedmagnesium, the range of 10 to 100° C. is preferred.

The reaction temperature for adding the cyclopentenone represented bythe formula (3) after the reaction with a magnesium compound or anorganic lithium compound is usually in the range of −80° C. to theboiling point of a solvent, preferably −50 to 60° C.

A solvent used in the reaction is inert to the reaction is used. Such asolvent includes, for example, aromatic hydrocarbon solvents such asbenzene, toluene, xylene and the like; aliphatic hydrocarbon solventssuch as hexane, heptane and the like; ether solvents such as diethylether, tetrahydrofuran, 1,4-dioxane and the like; amide solvents such ashexamethylphosphoric triamide, dimethylformamide and the like. One or amixture of two or more of the solvents is used. The amount of a solventto be used is usually in the range of 1 to 200 times, preferably 3 to 50times the weight of the halogen compound represented by the formula (2).

After the reaction, water is added to the resulting reaction mixture,and the mixture is then separated into an organic layer and an aqueouslayer to give a solution of the objective compound as the organic layer.When the organic layer and the aqueous layer can not be easily separateddue to use of a solvent compatible with water or use of a small amountof a solvent in said reaction, the separation may be carried out afteraddition of a water-insoluble organic solvent such as toluene, ethylacetate, chlorobenzene and the like to the reaction mixture. A solutionof the cyclopentenols of the formula (4) thus-obtained may be used inthe next step as it is, or the cyclopentenols may be purified from saidsolution and then used in the next step. The cyclopentenols representedby the formula (4) can be purified, for example, by washing saidsolution with water, drying said solution, and then distilling off thesolvent, and further by methods such as recrystallization, distillation,column chromatography treatment and the like.

The cyclopentenols represented by the formula (4) thus-obtained include1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(2-ethyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(2-phenyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(dimethoxymethyl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(1,1-dimethoxyethyl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(1,1-dimethoxypropyl)-2-(1-hydroxy-2-phenylindan-1-yl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2,3-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-3,4-dimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2,3,4-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(2-hydroxy-2,4,5-trimethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-3-tert-butyl-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-3-dimethylamino-2-cyclopentenyl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-methylindan-1-yl)benzene,1-(1,1-dimethoxy-1-phenylmethyl)-2-(1-hydroxy-2-phenylindan-1-yl)benzeneand the like. Similarly the above-mentioned compounds in which benzeneis changed to substituted benzene or substituted naphthalene and thelike are also exemplified.

The second step is a step of reacting the cyclopentenols of the formula(4) with an acid to give the carbonyl compound (a substitutedcyclopentadiene ligand) represented by the formula (1).

An acid to be used in the above reaction includes inorganic acids suchas hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid andthe like; carboxylic acids such as formic acid, acetic acid,chloroacetic acid, trifluoroacetic acid, propionic acid, valeric acid,benzoic acid and the like; sulfonic acids such as methanesulfonic acid,trifluoromethanesulfonic acid, benzenesulfonic acid, toluenesulfonicacid and the like. These acids can be used alone or as a mixture or adiluted solution such as an aqueous solution. The amount of an acid tobe used is not specifically limited.

The above reaction is usually carried out in the presence of a solventand produces the carbonyl compound represented by the formula (1) havingcyclopentadiene structure by addition of an acid to the cyclopentenolrepresented by the formula (4). The reaction is carried out in the rangeof −20° C. to the boiling point of a solvent, preferably 0 to 80° C.

A solvent used in the reaction includes aromatic hydrocarbon solventssuch as benzene, toluene, xylene and the like; aliphatic hydrocarbonsolvents such as hexane, heptane and the like; ether solvents such asdiethyl ether, tetrahydrofuran, 1,4-dioxane and the like; amide solventssuch as hexamethylphosphoric triamide, dimethylformamide and the like;alcohol solvents such as methanol, ethanol, propanol, butanol and thelike; ketone solvents such as acetone, cyclopentanone, methyl isobutylketone and the like; and water. One or a mixture of two or more of thesesolvents is used. The solvents may be homogeneous system or two-phasesystem. The amount of a solvent to be used is usually in the range of 1to 200 parts by weight, preferably 5 to 30 parts by weight relative tothe 1 part by weight of the halogen compound represented by the formula(2).

After the reaction, if needed, water is added to the resulting reactionmixture. The mixture is then separated into an organic layer and anaqueous layer to give a solution of the objective compound as theorganic layer. When the organic layer and the aqueous layer can not beeasily separated due to use of a solvent compatible with water or use ofa small amount of a solvent in said reaction, the separation may becarried out after addition of a water-insoluble organic solvent such astoluene, ethyl acetate, chlorobenzene and the like to the reactionmixture. The carbonyl compound represented by the formula (1) ispurified, for example, by washing said solution with water, drying saidsolution, and then distilling off the solvent, and further by methodssuch as recrystallization, distillation, column chromatography treatmentand the like.

In J. Org. Chem., 1974, 39, 829 and Aust. J. Chem., 1993, 46, 1515,2-(inden-1-yl)benzaldehyde is disclosed. However, said compound issynthesized by oxidation of 3,6-dibenzotricyclo[3,3,0,0]octadiene withchromic acid and as a result, there is a problem of difficulty inobtaining the starting material 3,6-dibenzotricyclo[3,3,0,0]octadiene.In Chem. Ber., 1992, 125, 1461-1469,2-(2-benzyl-3-phenyl-1H-inden-1-yl)benzaldehyde is described as aby-product in synthesis of a polyindane compound.

Specific examples of the carbonyl compound represented by the formula(1) include the following compounds:

2-(cyclopentadienyl)benzaldehyde,2-(2-methylcyclopentadienyl)benzaldehyde,2-(3-methylcyclopentadienyl)benzaldehyde,2-(2,3-dimethylcyclopentadienyl)benzaldehyde,2-(2,4-dimethylcyclopentadienyl)benzaldehyde,2-(3,4-dimethylcyclopentadienyl)benzaldehyde,2-(2,3,4-trimethylcyclopentadienyl)benzaldehyde,2-(2,4,5-trimethylcyclopentadienyl)benzaldehyde,2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde,2-(2-tert-butylcyclopentadienyl)benzaldehyde,2-(3-tert-butylcyclopentadienyl)benzaldehyde,2-(2-dimethylaminocyclopentadienyl)benzaldehyde,2-(3-dimethylaminocyclopentadienyl)benzaldehyde,2-(cyclopentadienyl)acetophenone,2-(2-methylcyclopentadienyl)acetophenone,2-(3-methylcyclopentadienyl)acetophenone,2-(2,3-dimethylcyclopentadienyl)acetophenone,2-(2,4-dimethylcyclopentadienyl)acetophenone,2-(3,4-dimethylcyclopentadienyl)acetophenone,2-(2,3,4-trimethylcyclopentadienyl)acetophenone,2-(2,4,5-trimethylcyclopentadienyl)acetophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone,2-(2-tert-butylcyclopentadienyl)acetophenone,2-(3-tert-butylcyclopentadienyl)acetophenone,2-(2-dimethylaminocyclopentadienyl)acetophenone,2-(3-dimethylaminocyclopentadienyl)acetophenone,2-(cyclopentadienyl)propiophenone,2-(2-methylcyclopentadienyl)propiophenone,2-(3-methylcyclopentadienyl)propiophenone,2-(2,3-dimethylcyclopentadienyl)propiophenone,2-(2,4-dimethylcyclopentadienyl)propiophenone,2-(3,4-dimethylcyclopentadienyl)propiophenone,2-(2,3,4-trimethylcyclopentadienyl)propiophenone,2-(2,4,5-trimethylcyclopentadienyl)propiophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)propiophenone,2-(2-tert-butylcyclopentadienyl)propiophenone,2-(3-tert-butylcyclopentadienyl)propiophenone,2-(2-dimethylaminocyclopentadienyl)propiophenone,2-(3-dimethylaminocyclopentadienyl)propiophenone,2-(cyclopentadienyl)benzophenone,2-(2-methylcyclopentadienyl)benzophenone,2-(3-methylcyclopentadienyl)benzophenone,2-(2,3-dimethylcyclopentadienyl)benzophenone,2-(2,4-dimethylcyclopentadienyl)benzophenone,2-(3,4-dimethylcyclopentadienyl)benzophenone,2-(2,3,4-trimethylcyclopentadienyl)benzophenone,2-(2,4,5-trimethylcyclopentadienyl)benzophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)benzophenone,2-(2-tert-butylcyclopentadienyl)benzophenone,2-(3-tert-butylcyclopentadienyl)benzophenone,2-(2-dimethylaminocyclopentadienyl)benzophenone,2-(3-dimethylaminocyclopentadienyl)benzophenone,3-(cyclopentadienyl)-2-naphtaldehyde,3-(2-methylcyclopentadienyl)-2-naphtaldehyde,3-(3-methylcyclopentadienyl)-2-naphtaldehyde,3-(2,3-dimethylcyclopentadienyl)-2-naphtaldehyde,3-(2,4-dimethylcyclopentadienyl)-2-naphtaldehyde,3-(3,4-dimethylcyclopentadienyl)-2-naphtaldehyde,3-(2,3,4-trimethylcyclopentadienyl)-2-naphtaldehyde,3-(2,4,5-trimethylcyclopentadienyl)-2-naphtaldehyde,3-(2,3,4,5-tetramethylcyclopentadienyl)-2-naphtaldehyde,3-(2-tert-butylcyclopentadienyl)-2-naphtaldehyde,3-(3-tert-butylcyclopentadienyl)-2-naphtaldehyde,3-(2-dimethylaminocyclopentadienyl)-2-naphtaldehyde,3-(3-dimethylaminocyclopentadienyl)-2-naphtaldehyde,3-(cyclopentadienyl)-2-acetylnaphthalene,3-(2-methylcyclopentadienyl)-2-acetylnaphthalene,3-(3-methylcyclopentadienyl)-2-acetylnaphthalene,3-(2,3-dimethylcyclopentadienyl)-2-acetylnaphthalene,3-(2,4-dimethylcyclopentadienyl)-2-acetylnaphthalene,3-(3,4-dimethylcyclopentadienyl)-2-acetylnaphthalene,3-(2,3,4-trimethylcyclopentadienyl)-2-acetylnaphthalene,3-(2,4,5-trimethylcyclopentadienyl)-2-acetylnaphthalene,3-(2,3,4,5-tetramethylcyclopentadienyl)-2-acetylnaphthalene,3-(2-tert-butylcyclopentadienyl)-2-acetylnaphthalene,3-(3-tert-butylcyclopentadienyl)-2-acetylnaphthalene,3-(2-dimethylaminocyclopentadienyl)-2-acetylnaphthalene,3-(3-dimethylaminocyclopentadienyl)-2-acetylnaphthalene,3-(cyclopentadienyl)-2-propionylnaphthalene,3-(2-methylcyclopentadienyl)-2-propionylnaphthalene,3-(3-methylcyclopentadienyl)-2-propionylnaphthalene,3-(2,3-dimethylcyclopentadienyl)-2-propionylnaphthalene,3-(2,4-dimethylcyclopentadienyl)-2-propionylnaphthalene,3-(3,4-dimethylcyclopentadienyl)-2-propionylnaphthalene,3-(2,3,4-trimethylcyclopentadienyl)-2-propionylnaphthalene,3-(2,4,5-trimethylcyclopentadienyl)-2-propionylnaphthalene,3-(2,3,4,5-tetramethylcyclopentadienyl)-2-propionylnaphthalene,3-(2-tert-butylcyclopentadienyl)-2-propionylnaphthalene,3-(3-tert-butylcyclopentadienyl)-2-propionylnaphthalene,3-(2-dimethylaminocyclopentadienyl)-2-propionylnaphthalene,3-(3-dimethylaminocyclopentadienyl)-2-propionylnaphthalene,3-(cyclopentadienyl)-2-benzoylnaphthalene,3-(2-methylcyclopentadienyl)-2-benzoylnaphthalene,3-(3-methylcyclopentadienyl)-2-benzoylnaphthalene,3-(2,3-dimethylcyclopentadienyl)-2-benzoylnaphthalene,3-(2,4-dimethylcyclopentadienyl)-2-benzoylnaphthalene,3-(3,4-dimethylcyclopentadienyl)-2-benzoylnaphthalene,3-(2,3,4-trimethylcyclopentadienyl)-2-benzoylnaphthalene,3-(2,4,5-trimethylcyclopentadienyl)-2-benzoylnaphthalene,3-(2,3,4,5-tetramethylcyclopentadienyl)-2-benzoylnaphthalene,3-(2-tert-butylcyclopentadienyl)-2-benzoylnaphthalene,3-(3-tert-butylcyclopentadienyl)-2-benzoylnaphthalene,3-(2-dimethylaminocyclopentadienyl)-2-benzoylnaphthalene,3-(3-dimethylaminocyclopentadienyl)-2-benzoylnaphthalene,2-(cyclopentadienyl)-1-naphthaldehyde,2-(2-methylcyclopentadienyl)-1-naphthaldehyde,2-(3-methylcyclopentadienyl)-1-naphthaldehyde,2-(2,3-dimethylcyclopentadienyl)-1-naphthaldehyde,2-(2,4-dimethylcyclopentadienyl)-1-naphthaldehyde,2-(3,4-dimethylcyclopentadienyl)-1-naphthaldehyde,2-(2,3,4-trimethylcyclopentadienyl)-1-naphthaldehyde,2-(2,4,5-trimethylcyclopentadienyl)-1-naphthaldehyde,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-naphthaldehyde,2-(2-tert-butylcyclopentadienyl)-1-naphthaldehyde,2-(3-tert-butylcyclopentadienyl)-1-naphthaldehyde,2-(2-dimethylaminocyclopentadienyl)-1-naphthaldehyde,2-(3-dimethylaminocyclopentadienyl)-1-naphthaldehyde,2-(cyclopentadienyl)-1-acetylnaphthalene,2-(2-methylcyclopentadienyl)-1-acetylnaphthalene,2-(3-methylcyclopentadienyl)-1-acetylnaphthalene,2-(2,3-dimethylcyclopentadienyl)-1-acetylnaphthalene,2-(2,4-dimethylcyclopentadienyl)-1-acetylnaphthalene,2-(3,4-dimethylcyclopentadienyl)-1-acetylnaphthalene,2-(2,3,4-trimethylcyclopentadienyl)-1-acetylnaphthalene,2-(2,4,5-trimethylcyclopentadienyl)-1-acetylnaphthalene,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-acetylnaphthalene,2-(2-tert-butylcyclopentadienyl)-1-acetylnaphthalene,2-(3-tert-butylcyclopentadienyl)-1-acetylnaphthalene,2-(2-dimethylaminocyclopentadienyl)-1-acetylnaphthalene,2-(3-dimethylaminocyclopentadienyl)-1-acetylnaphthalene,2-(cyclopentadienyl)-1-propionylnaphthalene,2-(2-methylcyclopentadienyl)-1-propionylnaphthalene,2-(3-methylcyclopentadienyl)-1-propionylnaphthalene,2-(2,3-dimethylcyclopentadienyl)-1-propionylnaphthalene,2-(2,4-dimethylcyclopentadienyl)-1-propionylnaphthalene,2-(3,4-dimethylcyclopentadienyl)-1-propionylnaphthalene,2-(2,3,4-trimethylcyclopentadienyl)-1-propionylnaphthalene,2-(2,4,5-trimethylcyclopentadienyl)-1-propionylnaphthalene,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-propionylnaphthalene,2-(2-tert-butylcyclopentadienyl)-1-propionylnaphthalene,2-(3-tert-butylcyclopentadienyl)-1-propionylnaphthalene,2-(2-dimethylaminocyclopentadienyl)-1-propionylnaphthalene,2-(3-dimethylaminocyclopentadienyl)-1-propionylnaphthalene,2-(cyclopentadienyl)-1-benzoylnaphthalene,2-(2-methylcyclopentadienyl)-1-benzoylnaphthalene,2-(3-methylcyclopentadienyl)-1-benzoylnaphthalene,2-(2,3-dimethylcyclopentadienyl)-1-benzoylnaphthalene,2-(2,4-dimethylcyclopentadienyl)-1-benzoylnaphthalene,2-(3,4-dimethylcyclopentadienyl)-1-benzoylnaphthalene,2-(2,3,4-trimethylcyclopentadienyl)-1-benzoylnaphthalene,2-(2,4,5-trimethylcyclopentadienyl)-1-benzoylnaphthalene,2-(2,3,4,5-tetramethylcyclopentadienyl)-1-benzoylnaphthalene,2-(2-tert-butylcyclopentadienyl)-1-benzoylnaphthalene,2-(3-tert-butylcyclopentadienyl)-1-benzoylnaphthalene,2-(2-dimethylaminocyclopentadienyl)-1-benzoylnaphthalene,2-(3-dimethylaminocyclopentadienyl)-1-benzoylnaphthalene,2-(cyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2-methylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(3-methylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2,3-dimethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2,4-dimethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(3,4-dimethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2,3,4-trimethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2,4,5-trimethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2-tert-butylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(3-tert-butylcyclopentadienyl)-5-tert-butylbenzaldehyde,2-(2-dimethylaminocyclopentadienyl)-5-tert-butylbenzaldehyde,2-(3-dimethylaminocyclopentadienyl)-5-tert-butylbenzaldehyde,2-(cyclopentadienyl)-5-tert-butylacetophenone,2-(2-methylcyclopentadienyl)-5-tert-butylacetophenone,2-(3-methylcyclopentadienyl)-5-tert-butylacetophenone,2-(2,3-dimethylcyclopentadienyl)-5-tert-butylacetophenone,2-(2,4-dimethylcyclopentadienyl)-5-tert-butylacetophenone,2-(3,4-dimethylcyclopentadienyl)-5-tert-butylacetophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-tert-butylacetophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-tert-butylacetophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-tert-butylacetophenone,2-(2-tert-butylcyclopentadienyl)-5-tert-butylacetophenone,2-(3-tert-butylcyclopentadienyl)-5-tert-butylacetophenone,2-(2-dimethylaminocyclopentadienyl)-5-tert-butylacetophenone,2-(3-dimethylaminocyclopentadienyl)-5-tert-butylacetophenone,2-(cyclopentadienyl)-5-tert-butylpropiophenone,2-(2-methylcyclopentadienyl)-5-tert-butylpropiophenone,2-(3-methylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2,3-dimethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2,4-dimethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(3,4-dimethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2-tert-butylcyclopentadienyl)-5-tert-butylpropiophenone,2-(3-tert-butylcyclopentadienyl)-5-tert-butylpropiophenone,2-(2-dimethylaminocyclopentadienyl)-5-tert-butylpropiophenone,2-(3-dimethylaminocyclopentadienyl)-5-tert-butylpropiophenone,2-(cyclopentadienyl)-5-tert-butylbenzophenone,2-(2-methylcyclopentadienyl)-5-tert-butylbenzophenone,2-(3-methylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2,3-dimethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2,4-dimethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(3,4-dimethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2-tert-butylcyclopentadienyl)-5-tert-butylbenzophenone,2-(3-tert-butylcyclopentadienyl)-5-tert-butylbenzophenone,2-(2-dimethylaminocyclopentadienyl)-5-tert-butylbenzophenone,2-(3-dimethylaminocyclopentadienyl)-5-tert-butylbenzophenone,2-(cyclopentadienyl)-5-chlorobenzaldehyde,2-(2-methylcyclopentadienyl)-5-chlorobenzaldehyde,2-(3-methylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2,3-dimethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2,4-dimethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(3,4-dimethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2,3,4-trimethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2,4,5-trimethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2-tert-butylcyclopentadienyl)-5-chlorobenzaldehyde,2-(3-tert-butylcyclopentadienyl)-5-chlorobenzaldehyde,2-(2-dimethylaminocyclopentadienyl)-5-chlorobenzaldehyde,2-(3-dimethylaminocyclopentadienyl)-5-chlorobenzaldehyde,2-(cyclopentadienyl)-5-chloroacetophenone,2-(2-methylcyclopentadienyl)-5-chloroacetophenone,2-(3-methylcyclopentadienyl)-5-chloroacetophenone,2-(2,3-dimethylcyclopentadienyl)-5-chloroacetophenone,2-(2,4-dimethylcyclopentadienyl)-5-chloroacetophenone,2-(3,4-dimethylcyclopentadienyl)-5-chloroacetophenone,2-(2,3,4-trimethylcyclopentadienyl-5-chloroacetophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-chloroacetophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-chloroacetophenone,2-(2-tert-butylcyclopentadienyl)-5-chloroacetophenone,2-(3-tert-butylcyclopentadienyl)-5-chloroacetophenone,2-(2-dimethylaminocyclopentadienyl)-5-chloroacetophenone,2-(3-dimethylaminocyclopentadienyl)-5-chloroacetophenone,2-(cyclopentadienyl)-5-chloropropiophenone,2-(2-methylcyclopentadienyl)-5-chloropropiophenone,2-(3-methylcyclopentadienyl)-5-chloropropiophenone,2-(2,3-dimethylcyclopentadienyl)-5-chloropropiophenone,2-(2,4-dimethylcyclopentadienyl)-5-chloropropiophenone,2-(3,4-dimethylcyclopentadienyl)-5-chloropropiophenone,2-(2,3,4-trimethylcyclopentadienyl-5-chloropropiophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-chloropropiophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-chloropropiophenone,2-(2-tert-butylcyclopentadienyl)-5-chloropropiophenone,2-(3-tert-butylcyclopentadienyl)-5-chloropropiophenone,2-(2-dimethylaminocyclopentadienyl)-5-chloropropiophenone,2-(3-dimethylaminocyclopentadienyl)-5-chloropropiophenone,2-(cyclopentadienyl)-5-chlorobenzophenone,2-(2-methylcyclopentadienyl)-5-chlorobenzophenone,2-(3-methylcyclopentadienyl)-5-chlorobenzophenone,2-(2,3-dimethylcyclopentadienyl)-5-chlorobenzophenone,2-(2,4-dimethylcyclopentadienyl)-5-chlorobenzophenone,2-(3,4-dimethylcyclopentadienyl)-5-chlorobenzophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-chlorobenzophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-chlorobenzophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-chlorobenzophenone,2-(2-tert-butylcyclopentadienyl)-5-chlorobenzophenone,2-(3-tert-butylcyclopentadienyl)-5-chlorobenzophenone,2-(2-dimethylaminocyclopentadienyl)-5-chlorobenzophenone,2-(3-dimethylaminocyclopentadienyl)-5-chlorobenzophenone,2-(cyclopentadienyl)-5-methoxybenzaldehyde,2-(2-methylcyclopentadienyl)-5-methoxybenzaldehyde,2-(3-methylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2,3-dimethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2,4-dimethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(3,4-dimethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2,3,4-trimethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2,4,5-trimethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2-tert-butylcyclopentadienyl)-5-methoxybenzaldehyde,2-(3-tert-butylcyclopentadienyl)-5-methoxybenzaldehyde,2-(2-dimethylaminocyclopentadienyl)-5-methoxybenzaldehyde,2-(3-dimethylaminocyclopentadienyl)-5-methoxybenzaldehyde,2-(cyclopentadienyl)-5-methoxyacetophenone,2-(2-methylcyclopentadienyl)-5-methoxyacetophenone,2-(3-methylcyclopentadienyl)-5-methoxyacetophenone,2-(2,3-dimethylcyclopentadienyl)-5-methoxyacetophenone,2-(2,4-dimethylcyclopentadienyl)-5-methoxyacetophenone,2-(3,4-dimethylcyclopentadienyl)-5-methoxyacetophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-methoxyacetophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-methoxyacetophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-methoxyacetophenone,2-(2-tert-butylcyclopentadienyl)-5-methoxyacetophenone,2-(3-tert-butylcyclopentadienyl)-5-methoxyacetophenone,2-(2-dimethylaminocyclopentadienyl)-5-methoxyacetophenone,2-(3-dimethylaminocyclopentadienyl)-5-methoxyacetophenone,2-(cyclopentadienyl)-5-methoxypropiophenone,2-(2-methylcyclopentadienyl)-5-methoxypropiophenone,2-(3-methylcyclopentadienyl)-5-methoxypropiophenone,2-(2,3-dimethylcyclopentadienyl)-5-methoxypropiophenone,2-(2,4-dimethylcyclopentadienyl)-5-methoxypropiophenone,2-(3,4-dimethylcyclopentadienyl)-5-methoxypropiophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-methoxypropiophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-methoxypropiophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-methoxypropiophenone,2-(2-tert-butylcyclopentadienyl)-5-methoxypropiophenone,2-(3-tert-butylcyclopentadienyl)-5-methoxypropiophenone,2-(2-dimethylaminocyclopentadienyl)-5-methoxypropiophenone,2-(3-dimethylaminocyclopentadienyl)-5-methoxypropiophenone,2-(cyclopentadienyl)-5-methoxybenzophenone,2-(2-methylcyclopentadienyl)-5-methoxybenzophenone,2-(3-methylcyclopentadienyl)-5-methoxybenzophenone,2-(2,3-dimethylcyclopentadienyl)-5-methoxybenzophenone,2-(2,4-dimethylcyclopentadienyl)-5-methoxybenzophenone,2-(3,4-dimethylcyclopentadienyl)-5-methoxybenzophenone,2-(2,3,4-trimethylcyclopentadienyl)-5-methoxybenzophenone,2-(2,4,5-trimethylcyclopentadienyl)-5-methoxybenzophenone,2-(2,3,4,5-tetramethylcyclopentadienyl)-5-methoxybenzophenone,2-(2-tert-butylcyclopentadienyl)-5-methoxybenzophenone,2-(3-tert-butylcyclopentadienyl)-5-methoxybenzophenone,2-(2-dimethylaminocyclopentadienyl)-5-methoxybenzophenone,2-(3-dimethylaminocyclopentadienyl)-5-methoxybenzophenone,2-(cyclopentadienyl)-5-methoxybenzophenone,2-(methylcyclopentadienyl)-5-methoxybenzophenone,2-(dimethylcyclopentadienyl)-5-methoxybenzophenone,2-(trimethylcyclopentadienyl)-5-methoxybenzophenone,2-(tetramethylcyclopentadienyl)-5-methoxybenzophenone,2-(tert-butylcyclopentadienyl)-5-methoxybenzophenone,2-(dimethylaminocyclopentadienyl)-5-methoxybenzophenone and the like.

EXAMPLES

The following Examples illustrate the present invention specifically,but not limit the present invention.

In the Tables 1 to 5, the following abbreviations are used.

TIBA: triisobutylaluminumMMAO: modified methyl aluminoxane (methyl aluminoxane modified byaddition of triisobutylaluminum)AB: dimethylanilinium tetrakis(pentafluorophenyl)borateCB: triphenylmethyl tetrakis(pentafluorophenyl)boratePE: polyethyleneTm: the melting point of a polymer

Example 1 Synthesis of1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene

Under a nitrogen atmosphere, a solution of2-(2-methyl-1,3-dioxolan-2-yl)-bromobenzene (1.22 g, 5.0 mmol) intetrahydrofuran (7.3 g) was cooled to −10° C. and a solution ofn-butyllithium in n-hexane (1.56 M, 3.4 mL) was added dropwise thereto.After keeping the temperature for 1 hr, a solution of2,3,4,5-tetramethylcyclopentenone (0.73 g, 5.3 mmol) in tetrahydrofuran(4.9 g) was added dropwise to the mixture. After raising the temperatureto 25° C., the mixture was stirred for 3 hrs. After quenching thereaction by addition of toluene and water, the aqueous layer wasremoved. The obtained organic layer was washed with saturated brine andthen dried over sodium sulfate, and the solvent was removed. Afterconcentration, the residue was washed with cooled hexane to give1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene(0.53 g, yield 35.0%).

¹H-NMR (CDCl₃): δ 7.65 (1H), 7.15 (3H), 5.83 (1H), 4.08 (1H), 3.89 (2H),2.34 (1H), 1.95 (3H, 1.82 (1H), 1.68 (3H), 1.36 (3H), 1.09 (3H), 1.03(3H);

MS (EI) m/z 284 (M-H₂O), 269, 239, 222, 207, 192, 178, 165.

Example 2 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-acetophenone

Under a nitrogen atmosphere, a solution of2-(2-methyl-1,3-dioxolan-2-yl)-bromobenzene (24.31 g, 100.0 mmol) indiethyl ether (146 g) was cooled to −70° C. and a solution ofn-butyllithium in n-hexane (1.56 M, 67.3 mL) was added dropwise thereto.After keeping the temperature for 1 hr, a solution of2,3,4,5-tetramethylcyclopentenone (14.51 g, 5.3 mmol) in diethyl ether(97 g) was added dropwise to the mixture. After raising the temperatureto 25° C., the mixture was stirred for 3 hrs. After quenching thereaction by addition of toluene and water, the aqueous layer wasremoved. The obtained organic layer was washed with saturated brine andthen dried over sodium sulfate. The solvent was removed to give a crudeproduct of1-(2-methyl-1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene.To the obtained crude product were added tetrahydrofuran (320 g), 3%aqueous hydrochloric acid solution (80 g) and acetone (32 g) and themixture was stirred at 25° C. for 24 hrs. After the reaction, toluenewas added to the reaction mixture. The organic layer was washed withwater and saturated brine and dried over sodium sulfate, and the solventwas removed. The residue was purified by silica gel columnchromatography to give2-(2,3,4,5-tetramethylcyclopentadienyl)acetophenone (10.00 g, yield41.6%).

¹H-NMR (CDCl₃): δ 7.51 (1H), 7.43 (1H), 7.28 (1H), 7.15 (1H), 3.08-2.57(1H), 2.26 (3H), 1.92 (3H), 1.85 (3H), 1.81-1.63 (3H), 1.11 (3H);

MS (EI) m/z 284 (M⁺), 269, 239, 222, 207, 192, 178, 165.

Example 3 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-benzaldehyde

Under a nitrogen atmosphere, a solution of2-(1,3-dioxolan-2-yl)-bromobenzene (34.36 g, 150.0 mmol) in diethylether (206 g) was cooled to −70° C. and a solution of n-butyllithium inn-hexane (1.56 M, 100.96 mL) was added dropwise thereto. After keepingthe temperature for 1 hr, a solution of2,3,4,5-tetramethylcyclopentenone (21.77 g, 157.5 mmol) in diethyl ether(137 g) was added dropwise to the mixture. After raising the temperatureto 25° C., the mixture was stirred for 3 hrs. After quenching thereaction by addition of toluene and water, the aqueous layer wasremoved. The obtained organic layer was washed with saturated brine andthen dried over sodium sulfate. The solvent was removed to give a crudeproduct of1-(1,3-dioxolan-2-yl)-2-(1-hydroxy-2,3,4,5-tetramethyl-2-cyclopentenyl)benzene.To the obtained crude product were added tetrahydrofuran (770 g), 3%aqueous hydrochloric acid solution (385.2 g) and acetone (77 g) and themixture was stirred at 25° C. for 24 hrs. After the reaction, toluenewas added the reaction mixture. The organic layer was washed with waterand saturated brine and then dried over sodium sulfate, and the solventwas removed. The residue was purified by silica gel columnchromatography to give2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde (15.78 g, yield46.5%).

¹H-NMR (CDCl₃): δ 9.91 (1H), 7.97 (1H), 7.56 (1H), 7-37 (1H), 7.22 (1H),3.22-2.75 (1H), 1.94 (3H), 1.87 (3H), 1.74 (3H), 0.95 (3H);

MS (EI) m/z 226 (M⁺), 221, 193, 178, 165.

Example 4 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(2.26 g, 10.0 mmol) in ethanol (29.0 mL) was added sodium borohydride(0.42 g, 11.0 mmol) at room temperature and the mixture was stirred for3 hrs. To the reaction mixture solution were added toluene (20.0 mL) anddeionized water (20.0 mL) to separate an organic layer and an aqueouslayer. The organic layer was dried over sodium sulfate and the solventwas then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol (2.23 g, yield96.0%) as a pale oily substance.

¹H-NMR (CDCl₃): δ 7.47-6.82 (4H), 4.48 (2H), 3.05-2.70 (1H), 2.35 (1H),1.97 (3H), 1.85 (3H), 1.68 (3H), 1.22-0.91 (3H);

MS (EI) m/z 228 (M⁺), 213, 195, 180, 165, 128, 115.

Example 5 Synthesis of{2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl}phenylmethylalcohol

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(2.0 g, 8.80 mmol) in tetrahydrofuran (34.0 mL) was added dropwise a1.05 M solution of phenyllithium in cyclohexane and ether (17.7 mL) at−78° C. The temperature of the mixture was raised to room temperatureand the mixture was stirred for 4 hrs. To the reaction mixture solutionwere added deionized water (20.0 mL) and toluene (20.0 mL) to separatean organic layer and an aqueous layer. The organic layer was dried oversodium sulfate, then distilled to remove the solvent, and purified by asilica gel column (hexane/ethyl acetate=9/1) to give{2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl}phenylmethylalcohol (2.83g, yield 87.0%) as a pale yellow oily substance.

¹H-NMR (CDCl₃): δ 7.77-6.91 (4H), 6.45-5.55 (2H), 3.21-2.25 (1H),1.88-1.45 (9H), 1.16-0.82 (3H);

MS (EI) m/z 304 (M⁺), 286, 271, 256, 193, 165, 77.

Example 6 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumbis(dimethylamide) [Complex 1]

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol(0.3 g, 1.3 mmol) in toluene (5.2 mL) was added dropwise a solution oftetrakis(dimethylamido)titanium (0.29 g, 1.3 mmol) in toluene (1.7 mL)at −30° C. The mixture was stirred for 30 min at room temperature andthen at 110° C. for 5 hrs. The solvent was distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumbis(dimethylamide) (0.30 g, yield 83.3%).

¹H-NMR (C₆D₆): δ 7.25-6.88 (4H), 5.46 (2H), 3.16 (12H), 1.97 (6H), 1.86(6H).

Example 7 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitanium dichloride[Complex 2]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumbis(dimethylamide) (0.84 g, 3.1 mmol) in pentane (15.2 mL) was addeddropwise a solution of trimethylchlorosilane (3.67 g, 33.8 mmol) inpentane (5.0 mL) at 0° C. The mixture was stirred at room temperaturefor 15 hrs. 2-(2,3,4,5-Tetramethylcyclopentadienyl)benzyloxytitaniumdichloride (1.00 g, yield 94.3%) was obtained as an yellow solid.

¹H-NMR (C₆D₆): δ 7.06-6.64 (4H), 5.12 (2H), 2.16 (6H), 1.63 (6H).

Example 8

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto MMAO (100 μl, 1.0 M, Kanto Kagaku) and2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumbis(dimethylamide) (0.25 μmol) were added and polymerization was carriedout for 30 min. As a result of polymerization, a polymer having themolecular weight (Mw) of 2,360,000 and the molecular weight distribution(Mw/Mn) of 3.7 was produced in an amount of 7.36×10⁴ g per 1 mol oftitanium and per an hour.

Example 9

Polymerization was carried out in a similar manner as in Example 8,except that absolution of triisobutylaluminum in hexane (100 μL, 1.0 M,Kanto Kagaku) was used instead of MMAO and triphenylcarbeniumtetrakispentafluorophenylborate (0.75 μmol) was used. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 737,000and the molecular weight distribution (Mw/Mn) of 2.6 was produced in anamount of 6.56×10⁴ g per 1 mol of titanium and per an hour.

Example 10

Polymerization was carried out in a similar manner as in Example 8,except that 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumdichloride was used as a catalyst component. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 143,000and the molecular weight distribution (Mw/Mn) of 1.6 was produced in anamount of 1.65×10⁵ g per 1 mol of titanium and per an hour.

Example 11

Polymerization was carried out in a similar manner as in Example 8except that 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumdichloride was used as a catalyst component, a solution oftriisobutylaluminum in hexane (100 μL, 1.0 M, Kanto Kagaku) was usedinstead of MMAO and triphenylcarbenium tetrakispentafluorophenylborate(0.75 μmol) was used. As a result of polymerization, a polymer havingthe molecular weight (Mw) of 786,000 and the molecular weightdistribution (Mw/Mn) of 2.7 was produced in an amount of 2.69×10⁵ g per1 mol of titanium and per an hour.

Example 12

Polymerization was carried out in a similar manner as in Example 8,except that 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitaniumdichloride was used as a catalyst component, a solution oftriisobutylaluminum in hexane (100 μL, 1.0 M, Kanto Kagaku) was usedinstead of MMAO and dimethylanilinium tetrakispentafluorophenylborate(0.75 μmol) was used. As a result of polymerization, a: polymer havingthe molecular weight (Mw) of 674,000 and the molecular weightdistribution (Mw/Mn) of 2.4 was produced in an amount of 2.38×10⁵ g per1 mol of titanium and per an hour.

Example 13 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-phenylamine

Under a nitrogen atmosphere, aniline (31.5 mmol) was added dropwise to asolution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde (30.0mmol) in ethanol (90.0 mL) and the mixture was stirred at roomtemperature. After disappearance of the aldehyde was confirmed by gaschromatography, the solvent was distilled off under reduced pressure togiveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-phenylamine(9.00 g, yield 100%).

¹H-NMR (C₆D₆): δ 8.75-8.65 (1H), 7.42-6.96 (9H), 3.01-2.50 (1H),1.73-0.76 (12H).

MS (EI) m/z 301, 286, 270, 254, 195, 145.

Example 14 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamine

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-phenylamine(3.0 mmol) in ethanol (9.0 ml) was added sodium borohydride (4.5 mmol)and the mixture was reacted at room temperature for 3 hrs. Water andtoluene were then added to the mixture. The organic layer was dried andconcentrated. The obtained oily substance was purified by silica gelcolumn chromatography to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamine(0.60 g, yield 66.0%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.42-7.36 (1H), 7.22-7.08 (5H), 6.73-6.68 (1H),6.50-6.44 (2H), 4.06-4.01 (2H), 3.52-3.45 (1H), 3.01-2.53 (1H),1.79-1.58 (9H), 0.96-0.86 (3H);

MS (EI) m/z 303, 286, 210, 195.

Example 15 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) Complex 3

To a solutionN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamine(1.0 mmol) in toluene (5.3 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (1.0 mmol) in toluene (1.9 mL) at −78°C. Thereafter, the mixture was stirred at room temperature for 1 hr andthen at 100° C. for 5 hrs to give a red solution. The solvent wasdistilled off under reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) (0.30 g, yield 100%) as a red solid.

¹H-NMR (C₆D₆): δ 7.24-6.83 (9H), 4.44 (2H), 3.00 (12H), 1.94 (6H), 1.71(6H).

Example 16 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride [Complex 4]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) (5.0 mmol) in toluene (32.0 mL) was added asolution of trimethylsilyl chloride (55.0 mmol) in toluene (24.0 mL) at0° C. and the mixture was then stirred at room temperature for 16 hrs.The solvent was distilled off under reduced pressure and hexane (25.0mL) was added to the residue. A precipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride (2.18 g, yield 100%) as an orange solid.

¹H-NMR (C₆D₆): δ 7.46-7.43 (2H), 7.20-6.85 (7H), 4.64 (2H), 2.07 (6H),1.83 (6H).

Example 17 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium bis(dimethylamide) [Complex 5]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamine(3.0 mmol) in toluene (15.0 mL) was added dropwise a solution oftetrakis(dimethylamino)zirconium (3.0 mmol) in toluene (10.0 mL) at −78°C. Thereafter, the mixture was stirred at room temperature for 1 hr andthen at 100° C. for hrs to give a yellow solution. The solvent wasdistilled off under reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium bis(dimethylamide) (1.43 g, yield 100%) as a brown solid.

¹H-NMR (C₆D₆): δ 7.43-6.77 (9H), 4.26 (2H), 2.89 (12H), 1.95 (6H), 1.71(6H).

Example 18 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium dichloride [Complex 6]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium bis(dimethylamide) (3.0 mmol) in hexane (24.0 mL) was added asolution of trimethylsilyl chloride (33.0 mmol) in hexane (6.0 mL) at 0°C. and the mixture was then stirred at room temperature for 16 hrs. Aprecipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium dichloride (0.59 g, 47.0%) as a yellowish green powder.

¹H-NMR (C₆D₆): δ 7.48-7.44 (2H), 7.22-6.94 (7H), 4.64 (2H), 2.02 (6H),1.79 (6H)

<<Homopolymerization of Ethylene>>

Example 19

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto MMAO (250 μmol, 5.8 wt % Al, Tosoh-Akzo Corporation) andN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride (0.25 μmol) were added and polymerization wascarried out for 30 min. As a result of polymerization, a polymer havingthe molecular weight (Mw) of 1,030,000 and the molecular weightdistribution (Mw/Mn) of 2.1 was produced in an amount of 5.85×10⁵ g per1 mol of titanium and per an hour.

Example 20

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto a solution of triisobutylaluminum in hexane (100 μL, 1.0 M,Kanto Kagaku),N-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride (0.25 μmol) and triphenylcarbeniumtetrakispentafluorophenylborate (0.75 μmol) were added andpolymerization was carried out for 24 min. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 1,070,000and the molecular weight distribution (Mw/Mn) of 1.9 was produced in anamount of 1.70×10⁶ g per 1 mol of titanium and per an hour.

Example 21

Polymerization was carried out in a similar manner as in Example 20,except that dimethylanilinium tetrakispentafluorophenylborate was usedinstead of triphenylcarbenium tetrakispentafluorophenylborate and thatthe polymerization period was changed from 24 min to 21 min. As a resultof polymerization, a polymer having the molecular weight (Mw) of1,040,000 and the molecular weight distribution (Mw/Mn) of 2.3 wasproduced in an amount of 1.91×10⁶ g per 1 mol of titanium and per anhour.

Example 22

Polymerization was carried out in a similar manner as in Example 21,except that trispentafluorophenylborane was used instead oftriphenylcarbenium tetrakispentafluorophenylborate and that thepolymerization period was changed from 24 min to 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 172,000and the molecular weight distribution (Mw/Mn) of 2.1 was produced in anamount of 5.60×10⁴ g per 1 mol of titanium and per an hour.

Example 23

Polymerization was carried out in a similar manner as in Example 19,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride. As a result of polymerization, a polymer having themolecular weight (Mw) of 803,000 and the molecular weight distribution(Mw/Mn) of 1.8 was produced in an amount of 7.52×10⁴ g per 1 mol oftitanium and per an hour.

Example 24

Polymerization was carried out in a similar manner as in Example 20,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride and the stirring period was changed from 24 min to30 min. As a result of polymerization, a polymer having the molecularweight (Mw) of 766,000 and the molecular weight distribution (Mw/Mn) of1.7 was produced in an amount of 4.48×10⁵ g per 1 mol of titanium andper an hour.

Example 25

Polymerization was carried out in a similar manner as in Example 19,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium bis(dimethylamide) was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride. As a result of polymerization, a polymer having themolecular weight (Mw) of 916,000 and the molecular weight distribution(Mw/Mn) of 37.1 was produced in an amount of 5.52×10⁴ g per 1 mol oftitanium and per an hour.

Example 26

Polymerization was carried out in a similar manner as in Example 19,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium dichloride was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride. As a result of polymerization, a polymer having themolecular weight (Mw) of 78,700 and the molecular weight distribution(Mw/Mn) of 5.8 was produced in an amount of 4.51×10⁵ g per 1 mol oftitanium and per an hour.

Example 27

Polymerization was carried out in a similar manner as in Example 24,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium dichloride was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride. As a result of polymerization, a polymer having themolecular weight (Mw) of 9,190 and the molecular weight distribution(Mw/Mn) of 2.3 was produced in an amount of 8.38×10⁵ g per 1 mol oftitanium and per an hour.

Example 28

Polymerization was carried out in a similar manner as in Example 21,except thatN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidozirconium dichloride was used instead ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitaniumdichloride and that the stirring period was changed from 21 min to 30min. As a result of polymerization, a polymer having the molecularweight (Mw) of 10,600 and the molecular weight distribution (Mw/Mn) of3.3 was produced per 6.44×10 μg per 1 mol of titanium and per an hour.

<<Copolymerization of Ethylene-Hexene>>

Example 29

An autoclave was charged with toluene (5.0 mL) and hexene (5.00 μL)under nitrogen and the temperature was stabilized at 70° C. It was thencharged with ethylene until it was pressurized to 0.60 MPa, and thepressure was stabilized. Thereto a solution of triisobutylaluminum inhexane (100 μL, 1.0 M, Kanto Kagaku),N-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride (0.25 μmol) and triphenylcarbeniumtetrakispentafluorophenylborate (0.75 μmol) were added andpolymerization was carried out for 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 873,000and the molecular weight distribution (Mw/Mn) of 2.5 was produced in anamount of 1.06×10⁶ g per 1 mol of titanium and per an hour.

Example 30

Polymerization was carried out in a similar manner as in Example 29,except that dimethylanilinium tetrakispentafluorophenylborate was usedinstead of triphenylcarbenium tetrakispentafluorophenylborate. As aresult of polymerization, a polymer having the molecular weight (Mw) of492,000 and the molecular weight distribution (Mw/Mn) of 5.3 wasproduced in an amount of 1.07×10⁶ g per 1 mol of titanium and per anhour.

Example 31 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde phenylhydrazone

Under a nitrogen atmosphere, to a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde (20.0 mmol) inethanol (60.0 mL) was added dropwise phenylhydrazine (22.0 mmol) and themixture was stirred at room temperature for 2-hrs. The solvent wasdistilled off under reduced pressure and the residue was recrystallizedfrom hexane to give 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydephenylhydrazone (4.8 g, yield 76.3%).

¹H-NMR (C₆D₆): δ 8.13-8.08 (1H), 7.62-7.53 (2H), 7.30-7.23 (4H),7.10-7.06 (3H), 6.86-6.82 (1H), 3.13-2.73 (1H), 1.93-1.88 (5H),1.71-1.58 (4H), 1.20-0.91 (3H).

Example 32 Synthesis of Complex 7

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydephenylhydrazone (1.0 mmol) in toluene (5.3 mL) was added dropwise asolution of tetrakis(dimethylamino)titanium (1.0 mmol) in toluene (1.9mL) at −78° C. The mixture was stirred at room temperature for 1 hr andthen at 100° C. for 0.5 hrs to give a red solution. The solvent wasdistilled off under reduced pressure to give Complex 7 as a red solid(2.23 g, yield 100%).

¹H-NMR (C₆D₆): δ 8.55 (1H), 7.31-6.88 (9H), 3.18 (12H), 2.09 (6H), 1.50(6H).

Example 33 Synthesis of Complex 8

To a solution of Complex 7 (5.0 mmol) in toluene (32.0 mL) was addeddropwise a solution of trimethylsilyl-chloride (55.0 mmol) in toluene(24.0 mL) at 0° C. and the mixture was then stirred at room temperaturefor 16 hrs. The solvent was distilled off under reduced pressure andhexane (25.0 mL) was added to the residue. A precipitated solid wasfiltered to give Complex 8 as an orange solid (2.20 g, 99.5%).

¹H-NMR (C₆D₆): δ 8.05 (1H), 7.63-7.61 (2H), 7.13-6.84 (7H), 2.11 (6H),1.59 (6H).

Example 34 Synthesis of Complex 9

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydephenylhydrazone (3.0 mmol) in toluene (15.0 mL) was added dropwise asolution of tetrakis(dimethylamino)zirconium (3.0 mmol) in toluene (10.0mL) at −78° C. and the mixture was stirred at room temperature for 1 hrand then at 100° C. for 5 hrs to give a yellow solution. The solvent wasdistilled off under reduced pressure to give Complex 9 as a brown solid(1.47 g, yield 100%).

¹H-NMR (C₆D₆): δ 8.15 (1H), 7.28-6.90 (9H), 3.00 (12H), 2.09 (6H), 1.79(6H).

Example 35 Synthesis of Complex 10

To a solution of Complex 9 (3.0 mmol) in hexane (24.0 mL) was addeddropwise a solution of trimethylsilyl chloride (33.0 mmol) in hexane(6.0 mL) at 0° C. and the mixture was then stirred at room temperaturefor 20 hrs. A precipitated solid was filtered to give Complex 10 as ayellowish green powder (0.83 g, yield 58.1%).

¹H-NMR (C₆D₆): δ 7.94 (1H), 7.44-7.42 (2H), 7.16-6.86 (7H), 2.10 (6H),1.64 (6H).

Polymerization Example 36

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto MMAO (250 μmol, 5.8 wt % Al, Tosoh-Akzo Corporation) and Complex2 (0.25 μmol) were added and polymerization was carried out for 30 min.As a result of polymerization, a polymer having the molecular weight(Mw) of 453,000 and the molecular weight distribution (Mw/Mn) of 2.1 wasproduced in an amount of 1.07×10⁶ g per 1 mol of titanium and per anhour.

Example 37

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto a solution of triisobutylaluminum in hexane (100 μL, 1.0 M,Kanto Kagaku), Complex 2 (0.25 μmol) and triphenylcarbeniumtetrakispentafluorophenylborate (0.75 μmol) were added andpolymerization was carried out for 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 658,000and the molecular weight distribution (Mw/Mn) of 2.2 was produced in anamount of 1.11×10⁶ g per 1 mol of titanium and per an hour.

Example 38

Polymerization was carried out in a similar manner as in Example 37,except that dimethylanilinium tetrakispentafluorophenylborate was usedinstead of triphenylcarbenium tetrakispentafluorophenylborate. As aresult of polymerization, a polymer having the molecular weight (Mw) of611,000 and the molecular weight distribution (Mw/Mn) of 2.2 wasproduced in an amount of 1.07×10⁶ g per 1 mol of titanium and per anhour.

Example 39

Polymerization was carried out in a similar manner as in Example 36,except that Complex 1 was used instead of Complex 2. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 416,000and the molecular weight distribution (Mw/Mn) of 2.1 was produced in anamount of 2.42×10⁵ g per 1 mol of titanium and per an hour.

Example 40

Polymerization was carried out in a similar manner as in Example 37,except that Complex 4 was used instead of Complex 2. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 587,000and the molecular weight distribution (Mw/Mn) of 13.0 was produced in anamount of 5.26×10⁵ g per 1 mol of titanium and per an hour.

Example 41

Polymerization was carried out in a similar manner as in Example 38,except that Complex 4 was used instead of Complex 2. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 94,000 andthe molecular weight distribution (Mw/Mn) of 17.3 was produced in anamount of 4.91×10⁵ g per 1 mol of titanium and per an hour.

Example 42 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(8.86 g, 39.2 mmol) in tetrahydrofuran (150.0 mL) were addedmethoxyamine hydrochloride (4.25 g, 50.9 mmol), sodium acetate (4.18 g,50.9 mmol) and water, and the mixture was stirred at room temperaturefor 2 hrs.

To the reaction mixture solution were added ethyl acetate (20.0 mL) andwater (20.0 mL) to separate an organic layer and an aqueous layer. Theorganic layer was dried over sodium sulfate and the solvent was thendistilled off to giveO-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde oxime (8.85g, yield 88.5%) as a yellow oily substance.

To a solution of the obtainedO-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde oxime (4.00g, 15.7 mmol) in tetrahydrofuran (68.0 mL) was added dropwise a 1.5 Msolution of phenyllithium in cyclohexane/ether (60.0 mL) at −78° C. Thetemperature of the mixture was raised to room temperature and themixture was stirred for 5 hrs.

To the reaction mixture solution were added toluene (30.0 mL) and water(30.0 mL) to separate an organic layer and an aqueous layer. The organiclayer was dried over sodium sulfate and the solvent was then distilledoff to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine(4.40 g, yield 93.2%) as a brown oily substance.

¹H-NMR (CDCl₃): δ 9.53 (1H), 7.59-7.47 (9H), 2.83-2.12 (1H), 1.72 (3H),1.65 (3H), 1.59 (3H), 0.99-0.64 (3H);

MS (EI) m/z 301 (M⁺), 286, 270, 256, 165, 77.

Example 43 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine

According to a similar manner as in Example 42,O-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde oxime wassynthesized. To a solution ofO-methyl-2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde oxime (1.28g, 5.0 mmol) in tetrahydrofuran (68.0 mL) was added dropwise a 1.02 Msolution of tert-butyllithium in ether (60.0 mL) at −78° C. Thetemperature of the mixture was raised to room temperature and themixture was stirred for 5 hrs.

To the reaction mixture solution were added toluene (30.0 mL) anddeionized water (30.0 mL) to separate an organic layer and an aqueouslayer. The organic layer was dried over sodium sulfate and the solventwas then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine(1.34 g, yield 95.0%).

¹H-NMR (CDCl₃): δ 9.53 (1H), 7.36-7.02 (4H), 3.00-2.58 (1H), 1.85-1.83(3H), 1.70 (3H), 1.67 (3H), 1.10 (9H), 0.83-0.80 (3H);

MS (EI) m/z 281 (M⁺), 266, 252, 208, 194, 165.

Example 44 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) [Complex 11]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine(0.45 g, 1.5 mmol) in toluene was added dropwise a solution oftetrakis(dimethylamido)titanium (0.34 g, 1.5 mmol) in toluene (10.5 mL)at −30° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. the solvent was then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) (0.50 g, yield 76.9%).

¹H-NMR (C₆D₆): δ 7.88-6.98 (9H), 3.12 (6H), 3.10 (6H), 2.01 (6H), 1.92(6H).

Example 45 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride [Complex 12]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) (0.65 g, 1.5 mmol) in hexane (15.9 mL) was addeddropwise a solution of trimethylchlorosilane (1.63 g, 15.0 mmol) inhexane (3.9 mL) at 0° C. and the mixture was stirred at room temperaturefor 15 hrs. A precipitate was formed and then filtered to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride (0.50 g, yield 79.4%).

¹H-NMR (C₆D₆): δ 7.64-6.86 (9H), 2.18 (6H), 1.72 (6H).

Example 46 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidozirconiumbis(dimethylamide) [Complex 13]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimine(1.50 g, 5.3 mmol) in toluene (13.9 mL) was added dropwise a solution oftetrakis(dimethylamido)zirconium (1.43 g, 5.3 mmol) in toluene (3.5 mL)at −30° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. The solvent was then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidozirconiumbis(dimethylamide) (2.31 g, yield 91.3%).

¹H-NMR (C₆D₆): δ 7.96-6.98 (9H), 2.92 (12H), 2.01 (6H), 1.91 (6H).

Example 47 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumbis(dimethylamide) [Complex 14]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine(1.00 g, 3.5 mmol) in toluene (9.2 mL) was added dropwise a solution oftetrakis(dimethylamido)titanium (0.80 g, 3.5 mmol) in toluene (2.3 mL)at −30° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. The solvent was then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumbis(dimethylamide) (1.21 g, 81.8%).

¹H-NMR (C₆D₆): δ 7.77-6.92 (4H), 3.11 (12H), 2.04 (6H), 1.84 (6H), 1.45(9H).

Example 48 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride [Complex 15]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumbis(dimethylamide) (0.83 g, 2.0 mmol) in pentane (10.6 mL) was addeddropwise a solution of trimethylchlorosilane (2.39 g, 22.0 mmol) inpentane (2.7 mL) at 0° C., and the mixture was stirred at roomtemperature for 15 hrs. A precipitate was formed and then filtered togive2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride (0.51 g, yield 63.8%).

¹H-NMR (C₆D₆): δ 7.56-6.88 (4H), 2.18 (6H), 1.62 (6H), 1.23 (9H).

Example 49 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butylbenzenemethanimidozirconiumbis(dimethylamide) [Complex 16]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimine(2.37 g, 8.4 mmol) in toluene (21.9 mL) was added dropwise a solution oftetrakis(dimethylamido)zirconium (2.25 g, 8.4 mmol) in toluene (5.5 mL)at −30° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. The solvent was then distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidozirconiumbis(dimethylamide) (3.12 g, yield 80.8%).

¹H-NMR (C₆D₆): δ 7.84-6.92 (4H), 2.91 (12H), 2.02 (6H), 1.88 (6H), 1.47(9H).

Example 50 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidozirconiumdichloride [Complex 17]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidozirconiumbis(dimethylamide) (1.00 g, 2.2 mmol) in pentane (12.8 mL) was addeddropwise a solution of trimethylchlorosilane (2.60 g, 24.0 mol) inpentane (3.2 mL) at 0° C., and the mixture was stirred at roomtemperature for 28 hrs. A precipitate was formed and then filtered togive2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidozirconiumdichloride (0.35 g, yield 36.5%).

¹H-NMR (C₆D₆): δ7.64-6.78 (4H), 2.22 (3H), 2.18 (3H), 1.94 (3H), 1.92(3H), 1.46 (9H).

Example 51 Polymerization

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 70° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto a solution of triisobutylaluminum in hexane (100 μL, 1.0M, KantoKagaku), triphenylmethyl tetrakis(pentafluorophenyl)borate (0.375 μmol)and2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) (0.125 μmol) were added, and polymerization wascarried out for 30 min. As a result of polymerization, a polymer havingthe molecular weight (Mw) of 897,000 and the molecular weightdistribution (Mw/Mn) of 2.3 was produced in an amount of 4.08×10⁴ g per1 mol of titanium and per an hour.

Example 52

Polymerization was carried out in a similar manner as in Example 51,except that dimethylanilinium tetrakis(pentafluorophenyl)borate (0.375μmol) was used instead of triphenylmethyltetrakis(pentafluorophenyl)borate. As a result of polymerization, apolymer having the molecular weight (Mw) of 657,000 and the molecularweight distribution (Mw/Mn) of 2.5 was produced in an amount of 4.88×10⁴g per 1 mol of titanium and per an hour.

Example 53

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide). As a result of polymerization, a polymer having themolecular weight (Mw) of 968,000 and the molecular weight distribution(Mw/Mn) of 2.6 was produced in an amount of 5.70×10⁵ g per 1 mol oftitanium and per an hour.

Example 54

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumdichloride (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) and that dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.375 μmol) was used instead oftriphenylmethyl tetrakis(pentafluorophenyl)borate. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 1,150,000and the molecular weight distribution (Mw/Mn) of 2.6 was produced in anamount of 4.98×10⁵ g per 1 mol of titanium and per an hour.

Example 55

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumbis(dimethylamide) (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide). As a result of polymerization, a polymer having themolecular weight (Mw) of 1,370,000 and the molecular weight distribution(Mw/Mn) of 3.9 in an amount of 7.60×10⁴ g per 1 mol of titanium and peran hour.

Example 56

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumbis(dimethylamide) (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) and that dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.375 μmol) was used instead oftriphenylmethyl tetrakis(pentafluorophenyl)borate. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 1,250,000and the molecular weight distribution (Mw/Mn) of 3.3 was produced in anamount of 5.68×10⁴ g per 1 mol of titanium and per an hour.

Example 57

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide). As a result of polymerization, a polymer having themolecular weight: (Mw) of 1,830,000 and the molecular weightdistribution (Mw/Mn) of 1.7 was produced in an amount of 6.23×10⁵ g per1 mol of titanium and per an hour.

Example 58

Polymerization was carried out in a similar manner as in Example 51,except that2-(2,3,4,5-tetramethylcyclopentadienyl)-α-tert-butyl-benzenemethanimidotitaniumdichloride (0.125 μmol) was used instead of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-phenyl-benzenemethanimidotitaniumbis(dimethylamide) and that dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.375 μmol) was used instead oftriphenylmethyl tetrakis(pentafluorophenyl)borate. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 814,000and the molecular weight distribution (Mw/Mn) of 2.0 was produced in anamount of 3.81×10⁵ g per 1 mol of titanium and per an hour.

Example 59 Synthesis ofO-methyl-2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde oxime

To a solution of 2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde (11.32g, 50.0 mmol) in THF (170.0 mL) were added O-methylhydroxylaminehydrochloride (5.43 g, 65.0 mmol), sodium acetate (5.33 g, 65.0 mmol)and water (50.0 mL) at 25° C., and the mixture was stirred for 30 min.After the reaction, ethyl acetate and water were added thereto. Themixture was separated and the aqueous layer was removed. The obtainedorganic layer was dried over sodium sulfate and the solvent wasdistilled off under reduced pressure to giveO-methyl-2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde oxime (12.77 g,yield 100%).

¹H-NMR (CDCl₃): δ 7.97-7.90 (1H), 7.39-7.06 (4H), 3.94 (3H), 3.08-2.70(1H), 1.90 (3H), 1.84 (3H), 1.68 (3H), 0.88 (3H);

MS (EI) m/z 255 (M⁺), 240, 224, 209, 194.

Synthesis of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile

To a solution of diisopropylamine (1.52 g, 15.0 mmol) in THF (17.5 mL)was added dropwise 1.59 M n-butyllithium (9.4 mL, 15.0 mmol) at −78° C.The temperature of the mixture was raised to 20° C. to prepare lithiumdiisopropylamide. This reaction solution was cooled to −78° C. and asolution of O-methyl-2-(2,3,5-trimethylcyclopentadienyl)benzaldehydeoxime (1.28 g, 5.0 mmol) in tetrahydrofuran (4.3 mL) was added dropwisethereto.

After the temperature of the mixture was raised to room temperature, thereaction was quenched by adding toluene and water. The reaction mixturewas separated and the aqueous layer was removed. The obtained organiclayer was dried over sodium sulfate and the solvent was distilled offunder reduced pressure to give2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile (1.12 g, yield100%).

¹H-NMR (CDCl₃): δ 7.66 (1H), 7.52 (1H), 7.33-7.23 (2H), 3.38 (1H), 1.92(3H), 1.90 (3H), 1.87 (3H), 0.93 (3H);

MS (EI) m/z 223 (M⁺), 208, 193, 180, 165.

Example 60

To a solution of diisopropylamine (0.96 g, 9.5 mmol) in tetrahydrofuran(34.5 mL) was added dropwise 1.59 M n-butyllithium (6.0 mL, 9.5 mmol) at−78° C. The temperature of the mixture was then raised to 20° C. toprepare lithium diisopropylamide. The reaction solution was cooled to−78° C. and a solution ofO-methyl-2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde oxime (2.55 g,10.0 mmol) in tetrahydrofuran (8.6 mL) was added dropwise thereto. Thetemperature of the reaction solution was raised to room temperature.According to gas chromatography analysis,2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile was produced in63.9% yield.

Comparative Example 1

To 2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde (1.13 g, 5.0 mmol)were added acetic acid (22.60 g), sodium acetate (1.64 g, 20.0 mmol) andhydroxylamine hydrochloride (1.39 g, 20.0 mmol). The mixture was heatedto 110° C. and stirred to 3 hrs. According to gas chromatographyanalysis of the reaction solution,2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile was not produced.

Comparative Example 2

To 2-(2,3,5-trimethylcyclopentadienyl)benzaldehyde (1.13 g, 5.0 mmol)were added formic acid (17.0 g) and hydroxylamine hydrochloride (0.45 g,6.5 mmol). The mixture was heated to 110° C. and stirred for 30 min.According to gas chromatography analysis of the reaction solution,2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile was not produced.

Example 61 Synthesis of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumbis(dimethylamide) [Complex 18]

To a solution of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalcohol (1.00g, 3.2 mmol) in toluene (9.2 mL) was added a solution oftetrakis(dimethylamido)titanium (0.74 g, 3.2 mmol) in toluene (2.3 mL)at −78° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. The solvent was distilled off to give[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumbis(dimethylamide)(1.23 g, yield 86.6%).

¹H-NMR (C₆D₆): δ 7.16-6.96 (4H), 6.45 (1H), 3.09 (6H), 3.04 (6H), 2.07(3H), 1.97 (3H), 1.88 (3H), 1.85 (3H);

¹³C-NMR (C₆D₆): δ 147.9-121.4 (aroma), 86.0 (CH), 48.7, 47.5(NMe₂)_(12.1), 11.9, 11.1 (CH₃).

Example 62 Synthesis of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumdichloride [Complex 19]

To a solution of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumbis(dimethylamide)(0.7 g, 1.6 mmol) in pentane (8.9 mL) was addeddropwise a solution of tetramethylchlorosilane (1.91 g, 17.6 mmol) inpentane (2.2 mL) at 0° C. The mixture was stirred at room temperaturefor 15 hrs to give[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumdichloride (526.6 mg, yield 78.6%) as a yellow solid.

¹H-NMR (C₆D₆): δ 6.85-7.22 (4H), 6.32 (1H), 2.15 (3H), 2.10 (3H), 1.69(3H), 1.65 (3H);

MS (EI) m/z 420 (M⁺), 304, 286, 167, 113.

Example 63 Synthesis of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxyzirconiumbis(dimethylamide) [Complex 20]

To a solution of[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalcohol (0.97g, 3.1 mmol) in toluene (9.0 mL) was added dropwise a solution oftetrakis(dimethylamido)titanium (0.85 g, 3.1 mmol) in toluene (2.2 mL)at −78° C. The mixture was stirred at room temperature for 30 min andthen at 110° C. for 5 hrs. The solvent was distilled off to give[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxyzirconiumbis(dimethylamide) (1.02 g, yield 67.1%).

¹H-NMR (C₆D₆): δ 6.98-7.37 (4H), 6.35 (1H), 2.87 (6H), 2.85 (6H), 2.03(3H), 1.96 (3H), 1.89 (3H), 1.85 (3H);

¹³C-NMR (C₆D₆): δ 147.3-117.6 (aroma), 83.2 (CH), 48.7, 43.3 (NMe₂),11.1, 10.8, 10.6 (CH₃).

Example 64 Synthesis of N-[2-(1-indenyl)phenylmethyl]-N-phenylamine

To a solution of 2-(1-indenyl)benzaldehyde (7.0 mmol) in ethanol (19.4mL) was added dropwise aniline (7.3 mmol) under a nitrogen atmosphere.The mixture was stirred at room temperature. After disappearance of thealdehyde was confirmed by gas chromatography, The solvent was distilledoff under reduced pressure. After addition of ethanol (19.4 mL), sodiumborohydride (4.5 mmol) was added to the solution and the mixture wasreacted at room temperature for 3 hrs. Water and toluene were then addedto the reaction mixture. The organic layer was dried and concentrated.The obtained oily substance was purified by silica gel columnchromatography to give N-[2-(1-indenyl)phenylmethyl]-N-phenylamine (1.48g, yield 24.0%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.56-7.52 (3H), 7.36-7.07 (6H), 6.73-6.62 (2H),6.51-6.47 (3H), 4.26 (2H), 3.91-3.69 (1H), 3.51 (2H);

MS (EI) m/z 297 (M⁺), 264, 77.

Example 65 Synthesis of N-[2-(1-indenyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) [Complex 21]

To a solution of N-[2-(1-indenyl)phenylmethyl]-N-phenylamine (2.8 mmol)in toluene (15.2 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (2.8 mmol) in toluene (10.1 mL) at −78°C. The mixture was stirred at room temperature for 1 hr and then at 100°C. for 5 hrs to give a red solution. The solvent was distilled off underreduced pressure to give N-[2-(1-indenyl)phenylmethyl]-N-phenylamidotitanium bis(dimethylamide) (1.21 g) as a red solid.

¹H-NMR (C₆D₆): δ 7.41-7.00 (14H), 6.28-6.19 (1H), 5.84 (1H), 4.43 (1H),2.74 (6H), 2.48 (6H).

Example 66 Synthesis of N-[2-(1-indenyl)phenylmethyl]-N-phenylamidotitanium dichloride [Complex 22]

To a solution of N-[2-(1-indenyl)phenylmethyl]-N-phenylamido titaniumbis(dimethylamide) (2.8 mmol) in pentane (17.5 mL) was added dropwise asolution of trimethylsilyl chloride (30.8 mmol) in pentane (12.0 mL) at0° C. The mixture was then stirred at room temperature for 16 hrs. Aprecipitated solid was filtered to giveN-[2-(1-indenyl)phenylmethyl]-N-phenylamido titanium dichloride (0.24 g,yield 20.9%) as an orange solid.

¹H-NMR (C₆D₆): δ 7.41-7.00 (14H), 6.18 (1H), 5.21 (1H), 4.23 (1H);

MS (EI) m/z 413 (M⁺), 377, 297, 204.

Example 67 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amine

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(15.0 mmol) in ethanol (44.6 mL) were added dropwise 3,5-dimethylaniline(15.8 mmol) and acetic acid (1.5 mmol) under a nitrogen atmosphere. Themixture was stirred at room temperature. After disappearance of thealdehyde was confirmed by gas chromatography, sodium borohydride (19.5mmol) was added to the solution and reacted at room temperature for 3hrs. Water and toluene were then added to the reaction mixture. Theorganic layer was dried and concentrated. The obtained oily substancewas purified by silica gel column chromatography to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amine(4.88 g, yield 73.3%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.46-6.15 (7H), 4.30-4.08 (2H), 3.87-3.79 (1H),3.18-2.72 (1H), 2.33-0.95 (18H);

MS (EI) m/z 331 (M⁺), 210, 195.

Example 68 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)aminetitanium bis(dimethylamide) [Complex 23

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amine(4.0 mmol) in toluene (18.4 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (4.0 mmol) in toluene (12.2 mL) at −78°C. The mixture was stirred at room temperature for 1 hr and then at 100°C. for 5 hrs to give a red solution. The solvent was distilled off underreduced pressure to synthesizeN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)aminetitanium bis(dimethylamide) (2.08 g, yield 100%) as a red solid.

¹H-NMR (C₆D₆): δ 7.66-6.74 (7H), 4.48 (2H), 3.05 (12H), 1.94 (6H), 1.74(6H).

Example 69 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amidotitanium dichloride [Complex 24]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amidotitanium bis(dimethylamide) (4.0 mmol) in pentane (29.1 mL) was addeddropwise a solution of trimethylsilyl chloride (44.0 mmol) in pentane(19.0 mL) at 0° C. The mixture was then stirred at room temperature for16 hrs. A precipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(3,5-dimethylphenyl)amidotitanium dichloride (0.31 g, yield 15.6%) as an orange solid.

¹H-NMR (C₆D₆): δ 7.42-6.67 (7H), 4.73 (2H), 2.13 (6H), 2.05 (6H), 1.86(6H);

MS (EI) m/z 447 (M⁺), 411, 209.

Example 70 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,4,6-trimethylphenyl)amine

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(10.0 mmol) in ethanol (30.0 mL) were added dropwise acetic acid (1.0mmol) and 2,4,6-trimethylaniline (10.5 mmol) under a nitrogenatmosphere. The mixture was stirred at room temperature. Afterdisappearance of the aldehyde was confirmed by gas chromatography, thesolvent was distilled off under reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,4,6-trimethylphenyl)amine(3.43 g, yield 100%).

¹H-NMR (CDCl₃): δ 8.37-8.32 (1H), 8.21 (1H), 7.58-7.11 (3H), 6.86 (1H),3.15-2.67 (1H), 2.27 (3H), 2.12-0.94 (18H).

Example 71 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amine

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,4,6-trimethylphenyl)amine(10.0 mmol) in acetic acid (7.0 mL) was added sodium borohydride (13.0mmol). The mixture was reacted at room temperature for 1 hr. Water andtoluene were then added the reaction mixture. The organic layer wasdried and concentrated. The obtained oily substance was purified bysilica gel column chromatography to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amine(2.74 g, yield 69.5%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.67-7.04 (4H), 6.82-6.78 (2H), 3.91-3.77 (2H),3.10-2.62 (1H), 3.00-2.85 (1H), 2.28-0.88 (21H);

MS (EI) m/z 345 (M⁺), 210, 195.

Example 72 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amidozirconium bis(dimethylamide) [Complex 25]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amine(3.1 mmol) in toluene (11.1 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (3.1 mmol) in toluene (7.4 mL) at −78°C. The mixture was stirred at room temperature for 1 hr and then at 100°C. for 5 hrs to give a yellow solution. The solvent was distilled offunder reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amidozirconium bis(dimethylamide) (1.65 g, yield 100%) as a pale yellowsolid.

¹H-NMR (C₆D₆): δ 7.37-6.85 (6H), 4.34 (2H), 2.68 (12H), 2.16 (3H), 2.01(6H), 1.99 (12H);

MS (EI) m/z 521 (M⁺), 476, 432, 210.

Example 73 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amidozirconium dichloride [Complex 26]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amidozirconium bis(dimethylamide) (2.5 mmol) in pentane (13.6 mL) was addeddropwise a solution of trimethylsilyl chloride (27.5 mmol) in pentane(9.0 mL) at 0° C. The mixture was stirred at room temperature for 16hrs. A precipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,4,6-trimethylphenyl)amidozirconium dichloride (0.97 g, yield 77.0%) as a white solid.

¹H-NMR (C₆D₆) δ 7.42-7.09 (3H), 6.94-6.89 (1H), 6.80 (2H), 4.35 (2H),2.15 (6H), 2.07 (6H), 2.00 (3H), 1.86 (6H).

Example 74 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,6-diisopropylphenyl)amine

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(10.0 mmol) in ethanol (30.0 mL) were added dropwise acetic acid (1.0mmol) and 2,6-diisopropylaniline (10.5 mmol) under a nitrogenatmosphere. The mixture was stirred at room temperature. Afterdisappearance of the aldehyde was confirmed by gas chromatography, thesolvent was distilled off under reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,6-diisopropylphenyl)amine(3.85 g, yield 100%).

¹H-NMR (CDCl₃): δ 8.45-8.28 (1H), 8.14-8.10 (1H), 7.50-6.80 (6H),3.76-3.00 (1H), 3.00-2.85 (3H), 1.85-0.83 (24H).

Example 75 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amine

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,6-diisopropylphenyl)amine(10.0 mmol) in acetic acid (7.0 mL) was added sodium borohydride (13.0mmol). The mixture was reacted at room temperature for 1 hr. Water andtoluene were then added to the reaction mixture. The organic layer wasdried and concentrated. The obtained oily substance was purified bysilica gel column chromatography to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amine(3.19 g, yield 82.4%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.68-7.06 (7H), 3.91-3.77 (2H), 3.30-2.68 (1H),3.28-3.08 (2H), 3.08-2.91 (1H), 1.88-0.88 (24H);

MS (EI) m/z 387 (M⁺), 210, 195.

Example 76 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amidozirconium bis(dimethylamide) [Complex 27]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amine(3.0 mmol) in toluene (12.2 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (3.0 mmol) in toluene (8.1 mL) at −78°C. The mixture was stirred at room temperature 1 hr and then at 100° C.for 5 hrs to give a yellow solution. The solvent was distilled off underreduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amidozirconium bis(dimethylamide) (1.81 g, yield 100%) as a pale yellowsolid.

¹H-NMR (C₆D₆): δ 7.31-6.83 (7H), 4.43 (2H), 3.17 (2H), 2.64 (s, 12H),2.00 (6H), 1.98 (6H), 1.13 (6H), 1.00 (6H);

MS (EI) m/z 563 (M⁺), 518, 473, 431, 387, 210.

Example 77 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amidozirconium dichloride [Complex 28]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amidozirconium bis(dimethylamide) (2.5 mmol) in pentane (14.7 mL) was addeddropwise a solution of trimethylsilyl chloride (27.5 mmol) in pentane(10.0 mL) at 0° C. The mixture was then stirred at room temperature for16 hrs. A precipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-(2,6-diisopropylphenyl)amidozirconium dichloride (0.30 g, yield 22.0%) as a white solid.

¹H-NMR (C₆D₆): δ 7.20-6.76 (7H), 4.64 (2H), 3.01 (2H), 2.06 (6H), 1.87(6H), 1.43 (6H), 0.93 (6H);

MS (EI) m/z 547 (M⁺), 386, 319, 255, 210, 174.

Example 78 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-pentafluorophenylamine

Thionyl chloride (50.0 mmol) and pentafluoroaniline (5.0 mmol) weremixed under a nitrogen atmosphere at room temperature, and the volatilecomponent was distilled off under reduced pressure. To the mixture wasadded dropwise a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde (5.0 mmol) intoluene (13.8 mL) at room temperature. The mixture was stirred at roomtemperature. After disappearance of the aldehyde was confirmed by gaschromatography, the solvent was distilled off under reduced pressure togiveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-pentafluorophenylamine(2.10 g, yield 100%).

MS (EI) m/z 391 (M⁺), 209, 193, 179, 167, 77.

Example 79 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamine

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-pentafluorophenylamine(4.0 mmol) in acetic acid-(4.9 mL) was added sodium borohydride (5.2mmol). The mixture was reacted at room temperature for 3 hrs. Then, 5.0Maqueous NaOH solution and ether were added to the reaction mixture. Theorganic layer was dried and concentrated. The obtained oily substancewas purified by silica gel column chromatography to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamine(0.72 g, yield 34.2%) as a yellow oily substance.

¹H-NMR (CDCl₃): δ 7.48-7.06 (4H), 4.43-4.27 (2H), 3.85-3.70 (1H),3.00-2.70 (1H), 1.89-0.90 (12H); MS (EI) m/z 393 (M⁺), 210, 195, 180,165.

Example 80 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamidotitanium bis(dimethylamide) [Complex 29]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamine(1.3 mmol) in toluene (7.5 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (1.3 mmol) in toluene (5.0 mL) at −78°C. The mixture was stirred at room temperature for 1 hrs and then at100° C. for 5 hrs to give a red solution. The solvent was distilled offunder reduced pressure to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamidotitanium bis(dimethylamide) (0.72 g) as a red solid.

Example 81 Synthesis ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitanium dichloride [Complex 30]

To a solution ofN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamidotitanium bis(dimethylamide) (1.3 mmol) obtained by the above reaction inpentane (10.4 mL) was added dropwise a solution of trimethylsilylchloride (15.1 mmol) in pentane (7.0 mL) at 0° C. The mixture was thenstirred at room temperature for 16 hrs. A precipitated solid wasfiltered off and the obtained solution was concentrated. Pentane wasadded to the concentrate. A precipitated solid was filtered to giveN-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-pentafluorophenylamidotitanium dichloride (0.12 g, yield 17.4%) as an orange solid.

¹H-NMR (C₆D₆): δ 7.46-7.43 (2H), 7.20-6.85 (7H), 4.64 (2H), 2.07 (6H),1.83 (6H);

MS (EI) m/z 509 (M⁺), 473, 392, 209.

Example 82 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydepentafluorophenylhydrazone

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehyde(10.0 mmol) in ethanol (60.0 mL) was added dropwisepentafluorophenylhydrazine (11.0 mmol) under a nitrogen atmosphere. Themixture was stirred at room temperature for 2 hrs. The solvent wasdistilled off under reduced pressure and the residue was recrystallizedfrom hexane to give 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydepentafluorophenylhydrazone (4.00 g, yield 97.0%).

¹H-NMR (CDCl₃): δ 8.03-8.00 (1H), 7.71-6.91 (5H), 3.17-2.71 (1H),1.94-0.86 (12H);

MS (EI) m/z 406 (M⁺), 277, 244, 209.

Example 83 Synthesis of Complex 31

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzaldehydepentafluorophenylhydrazone (4.6 mmol) in toluene (19.0 mL) was addeddropwise a solution of tetrakis(dimethylamino)titanium (4.6 mmol) intoluene (13.0 mL) at −78° C. The mixture was stirred at room temperaturefor 1 hr and then at 100° C. for 5 hrs to give a red solution. Thesolvent was distilled off under reduced pressure to give Complex 28(2.37 g, yield 100%) as a red solid.

¹H-NMR (C₆D₆): δ 8.03-8.21 (1H), 7.71-6.99 (4H), 3.27 (12H), 2.77 (6H),2.60 (6H).

Example 84 Synthesis of Complex 32

To a solution of Complex 31 (4.4 mmol) in pentane (34.2 mL) was addeddropwise a solution of trimethylsilyl chloride (48.0 mmol) in toluene(23.0 mL) at 0° C. The mixture was then stirred at room temperature for16 hrs. A precipitated solid was filtered to give Complex 29 (0.72 g,yield 31.3%) as an orange solid.

¹H-NMR (C₆D₆): δ 8.53-8.50 (1H), 7.42-6.91 (4H), 2.16 (6H), 1.61 (6H).

MS (EI) m/z 522 (M⁺), 406, 342, 222, 209.

Example 85 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimine

To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzonitrile(6.3 mmol) in tetrahydrofuran (25.5 mL) was added dropwise a solution of2,4,6-trimethylphenyllithium (12.5 mmol) in tetrahydrofuran (55.6 mL) at−78° C. under a nitrogen atmosphere. The temperature of the mixture wasraised to room temperature and the mixture was stirred for 5 hrs. To thereaction mixture solution were added toluene and water to separate anorganic layer and an aqueous layer. The organic layer was dried and thesolvent was distilled off to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimine(2.34 g) as a brown oily substance.

MS (EI) m/z 342, 328, 312, 262.

Example 86 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimidotitaniumbis(dimethylamide) [Complex 33]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimine(1.0 mmol) in toluene (4.0 mL) was added dropwise a solution oftetrakis(dimethylamino)titanium (1.0 mmol) in toluene (2.0 mL) at −78°C. The mixture was stirred at room temperature for 1 hr and then at 100°C. for 5 hrs to give a red solution. The solvent was distilled off underreduced pressure to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimidotitanium bis(dimethylamide) (0.47 g).

Example 87 Synthesis of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimidotitanium dichloride [Complex 34]

To a solution of2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimidotitanium bis(dimethylamide) (1.0 mmol) in pentane (6.9 mL) was addeddropwise a solution of trimethylsilyl chloride (11.0 mmol) in pentane(5.0 mL) at 0° C. The mixture was then stirred at room temperature 16hrs. A precipitated solid was filtered to give2-(2,3,4,5-tetramethylcyclopentadienyl)-α-(2,4,6-trimethylphenyl)-benzenemethanimidotitanium dichloride (0.19 g, yield 44.0%) as an orange solid.

¹H-NMR (C₆D₆): δ 7.45-6.67 (6H), 2.43 (6H), 2.15 (3H), 2.08 (6H), 1.67(6H);

MS (EI) m/z 458 (M⁺), 423, 340, 278.

Polymerization Example 88 Polymerization Condition A-1

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 40° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto MMAO (250 μmol, 5.8 wt % A1, Tosoh-Akzo Corporation) (100 μmol)and[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumdichloride (0.10 μmol) were added and polymerization was carried out for30 min. As a result of polymerization, a polymer was produced in anamount of 4.00×10⁵ g per 1 mol of titanium and per an hour.

Example 89 Polymerization Condition B-1

Polymerization was carried out in a similar manner as in Example 88,except that a solution of triisobutylaluminum in hexane (40 μL, 1.0M,Kanto Kagaku) and pentafluorophenylborane (0.30 μmol) were used insteadof MMAO. As a result of polymerization, a polymer was produced in anamount of 1.00×10⁵ g per 1 mol of titanium and per an hour.

Example 90 Polymerization Condition C-1

Polymerization was carried out in a similar manner as in Example 88,except that a solution of triisobutylaluminum in hexane (40 μL, 1.0 M,Kanto Kagaku) and dimethylanilinium tetrakis(pentafluorophenyl)borate(0.30 μmol) were used instead of MMAO. As a result of polymerization, apolymer having the molecular weight (Mw) of 876,000, the molecularweight distribution (Mw/Mn) of 3.5 and Tm of 126.5° C. was produced inan amount of 3.10×10⁶ g per 1 mol of titanium and per an hour.

Example 91 Polymerization Condition D-1

Polymerization was carried out in a similar manner as in Example 88,except that a solution of triisobutylaluminum in hexane (40 μL, 1.0 M,Kanto Kagaku) and triphenylmethyl tetrakis(pentafluorophenyl)borate(0.30 μmol) were used instead of MMAO. As a result of polymerization, apolymer having the molecular weight (Mw) of 990,000, the molecularweight distribution (Mw/Mn) of 3.6 and Tm of 129.6° C. was produced inan amount of 2.60×10⁶ g per 1 mol of titanium and per an hour.

Example 92 Polymerization Condition A-2

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 40° C. It was then charged with ethyleneuntil it was pressurized to 0.60 MPa, and the pressure was stabilized.Thereto MMAO (250 μmol, 5.8 wt % A1, Tosoh-Akzo Corporation) (100 μmol)and[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethyl]-N-phenylamidotitaniumdichloride (0.10 μmol) were added and polymerization was carried out for30 min. As a result of polymerization, a polymer having the molecularweight (Mw) of 285,000, the molecular weight distribution (Mw/Mn) of 4.5and Tm of 85-9° C. was produced in an amount of 1.59×10⁶ g per 1 mol oftitanium and per an hour.

Example 93 Polymerization Condition A-3

Polymerization was carried out in a similar manner as in Example 92,except that the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 121,000,the molecular weight distribution (Mw/Mn) of 3.2 and Tm of 90.6° C. wasproduced in an amount of 1.01×10⁷ g per 1 mol of titanium and per anhour.

Example 94 Polymerization Condition B-2

An autoclave was charged with toluene (5.0 mL) and 1-hexene (0.50 μL)under nitrogen and the temperature was stabilized at 40° C. It was thencharged with ethylene until it was pressurized to 0.60 MPa, and thepressure was stabilized. Thereto a solution of triisobutylaluminum inhexane (40 μL, 1.0 M, Kanto Kagaku), pentafluorophenylborane (0.30 μmol)and N-[2-(1-indenyl)phenylmethyl]-N-phenylamido titanium dichloride(0.10 μmol) were added and polymerization was carried out for 30 min. Asa result of polymerization, a polymer having the molecular weight (Mw)of 1,360,000, the molecular weight distribution (Mw/Mn) of 8.4 and Tm of116.1° C. was produced in an amount of 2.25×10⁶ g per 1 mol of titaniumand per an hour.

Example 95 Polymerization Condition B-3

Polymerization was carried out in a similar manner as in Example 94,except that the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 817,000,the molecular weight distribution (Mw/Mn) of 19.3 and Tm of 122.2° C.was produced in an amount of 1.35×10⁷ g per 1 mol of titanium and per anhour.

Example 96 Polymerization Condition C-2

An autoclave was charged with toluene (5.0 mL) and 1-hexene (0.50 μL)under nitrogen and the temperature was stabilized at 40° C. It was thencharged with ethylene until it was pressurized to 0.60 MPa, and thepressure was stabilized. Thereto a solution of triisobutylaluminum inhexane (40 μL, 1.0 M, Kanto Kagaku), dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) and[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumdichloride (0.10 μmol) were added, and polymerization was carried outfor 30 min. As a result of polymerization, a polymer having themolecular weight (Mw) of 1,170,000, the molecular weight distribution(Mw/Mn) of 8.4 and Tm of 114.1° C. was produced in an amount of 1.00×10⁶g per 1 mol of titanium and per an hour.

Example 97 Polymerization Condition C-3

Polymerization was carried out in a similar manner as in Example 96,except that the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 530,000,the molecular weight distribution (Mw/Mn) of 7.7 and Tm of 116.0° C. wasproduced in an amount of 1.50×10⁶ g per 1 mol of titanium and per anhour.

Example 98 Polymerization Condition C-4

Polymerization was carried out in a similar manner as in Example 96,except that the polymerization temperature was 130° C. As a result ofpolymerization, a polymer was produced in an amount of 2.90×10⁵ g per 1mol of titanium and per an hour.

Example 99 Polymerization Condition D-2

An autoclave was charged with toluene (5.0 mL) and 1-hexene (0.50 μL)under nitrogen and the temperature was stabilized at 40° C. It was thencharged with ethylene until it was pressurized to 0.60 MPa, and thepressure was stabilized. Thereto a solution of triisobutylaluminum inhexane (40 μL, 1.0 M, Kanto Kagaku), triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) and[2-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]phenylmethylalkoxytitaniumdichloride (0.10 mol) were added, and polymerization was carried out for30 min. As a result of polymerization, a polymer having the molecularweight (Mw) of 1363,000, the molecular weight distribution (Mw/Mn) of10.5 and Tm of 115.8° C. was produced in an amount of 1.30×10⁶ g-per 1mol of titanium and per an hour.

Example 100 Polymerization Condition D-3

Polymerization was carried out in a similar manner as in Example 99,except that the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw) of 701,000,the molecular weight distribution (Mw/Mn) of 9.9 and Tm of =117.3° C.was produced in an amount of 1.20×10⁶ g per 1 mol of titanium and per anhour.

Example 101 Polymerization Condition D-4

Polymerization was carried out in a similar manner as in Example 99,except that the polymerization temperature was 130° C. As a result ofpolymerization, a polymer was produced in an amount of 2.00×10⁵ g per 1mol of titanium and per an hour.

The catalyst components, polymerization conditions, catalyst activities,reaction results of Examples 102 to 237 are shown in the followingTables 1 to 5.

TABLE 1 Homopolymerization of ethylene Polymerization Activity Examplecomplex condition (×10⁶ g PE/mol-cat/hr) 91 2 D-1 1.29 102 3 A-1 1.23103 3 C-1 1.83 104 3 D-1 3.66 105 4 A-1 12.87 106 4 B-1 4.35 107 4 C-19.09 108 4 D-1 4.17 109 7 C-1 1.38 110 7 D-1 1.47 111 8 A-1 2.76 112 8C-1 6.05 113 8 D-1 6.37 114 5 A-1 1.32 115 6 C-1 5.97 116 6 D-1 7.22 11712 C-1 5.97 118 12 D-1 7.22 119 15 C-1 1.89 120 15 D-1 2.13 121 10 C-12.91 122 10 D-1 3.36 123 18 C-1 3.12 124 18 D-1 2.61 125 30 A-1 4.05 12630 C-1 22.50 127 30 D-1 21.16 128 22 A-1 26.05 129 22 B-1 8.95 130 22C-1 6.32 131 22 D-1 5.61 132 25 A-1 5.58 133 25 C-1 7.49 134 25 D-113.50 135 27 A-1 3.72 136 27 C-1 17.59 137 27 D-1 19.52 138 26 A-1 8.81139 26 C-1 15.34 140 26 D-1 6.82 141 28 A-1 5.73 142 28 C-1 23.63 143 28D-1 34.66 144 24 A-1 4.47 145 24 B-1 3.12 146 24 C-1 7.50 147 24 D-19.29 148 31 A-1 1.98 149 31 C-1 2.91 150 31 D-1 3.33 151 34 C-1 12.13152 34 D-1 7.55

TABLE 2 Copolymerization of ethylene-hexene, co-catalyst MMAOPolymerization temperature, Tm, Example complex condition ° C. activity*Mw Mw/Mn ° C. 153 3 A-2 40 1.35 3,085,000 4.7 123.2 154 3 A-3 70 1.921,132,000 4.8 121.1 155 4 A-2 40 1.59 285,000 4.5 85.9 156 4 A-3 7010.19 121,000 3.2 90.6 157 8 A-2 40 2.70 1,444,000 4.7 117.4 158 8 A-370 1.95 1,173,000 10.1 119.4 159 5 A-3 70 1.92 163,000 9.5 126.9 160 6A-2 40 19.94 435,000 10.3 118.8 161 6 A-3 70 54.53 66,000 5.8 106.5 16230 A-2 40 3.42 1,624,000 7.4 109.9 163 30 A-3 70 4.87 1,486,000 39.7112.3 164 22 A-2 40 10.88 1,759,000 10.5 107.8 165 22 A-3 70 32.77778,000 22.1 110.1 166 25 A-2 40 4.59 336,000 4.3 118.9 167 25 A-3 7019.13 93,000 3.8 125 168 27 A-2 40 4.65 130,000 2.9 126.7 169 27 A-3 7027.21 44,000 3.6 123.9 170 26 A-2 40 14.23 246,000 3.2 125.9 171 26 A-370 39.04 124,000 3 124.5 172 28 A-2 40 9.12 123,000 3.2 128.6 173 28 A-370 58.76 46,000 2.9 125.5 174 24 A-2 40 3.42 1,596,000 8.7 125 175 24A-3 70 6.44 689,000 6.7 121.7 *×10⁶ g polymer/mol-cat/hr

TABLE 3 Copolymerization of ethylene-hexene, co-catalyst TIBA/(C₆F₅)3BPolymerization temperature, Tm, Example complex condition ° C. activityMw Mw/Mn ° C. 176 4 B-3 70 1.29 380,000 2.6 83.5 96 22 B-2 40 2.251,360,000 8.4 116.1 97 22 B-3 70 13.51 817,000 19.3 122.2 * ×10⁶ gpolymer/mol-cat/hr

TABLE 4 Copolymerization of ethylene-hexene, co-catalyst TIBA/ABPolymerization temperature, Tm, Example complex condition ° C. activity*Mw Mw/Mn ° C. 177 3 C-2 40 1.20 3,103,000 3.8 94.6 178 3 C-3 70 1.712,066,000 5.6 118.1 179 4 C-2 40 37.94 567,000 4.6 130.3 180 4 C-3 7075.10 202,000 3 108.5 181 4 C-4 130 47.57 178,000 3.2 100.2 182 7 C-2 401.23 1,526,000 5.8 117.3 183 7 C-3 70 1.32 1,041,000 3.9 119.3 184 8 C-240 8.24 1,204,000 4.4 116.6 185 8 C-3 70 4.07 1,337,000 5.3 117.4 186 6C-2 40 14.23 46,000 5.9 140.3 187 6 C-3 70 93.44 18,000 3.5 198.2 188 6C-4 130 19.12 114,000 6.3 119 189 12 C-3 70 1.71 1,636,000 19.9 121.8190 15 C-2 40 1.65 1,926,000 4.5 116.5 191 15 C-3 70 1.05 1,061,000 26.7112.9 192 10 C-2 40 4.08 417,000 115.3 119.2 193 18 C-2 40 0.991,170,000 8.4 114.1 194 18 C-3 70 1.47 530,000 7.7 116 195 30 C-2 405.79 1,517,000 2.4 97.5 196 22 C-2 40 6.08 973,000 17.7 113.6 197 22 C-370 61.03 603,000 23 118.2 198 22 C-4 130 0.96 460,000 6.7 124 199 25 C-240 8.29 157,000 4.2 123.8 200 25 C-3 70 33.76 133,000 3 124.2 201 27 C-240 14.46 489,000 4 123.8 202 26 C-2 40 19.89 156,000 3.4 128.1 203 26C-3 70 46.80 117,000 2.7 124.7 204 28 C-2 40 31.26 376,000 4.4 123 20528 C-3 70 42.77 967,000 2.5 121.6 206 24 C-2 40 4.89 749,000 21 121.4207 24 C-3 70 3.72 943,000 5.4 122 *×10⁶ g polymer/mol-cat/hr

TABLE 5 Copolymerization of ethylene-hexene, co-catalyst TIBA/CBPolymerization temperature, Tm, Example complex condition ° C. activity*Mw Mw/Mn ° C. 208 3 D-2 40 1.89 3,187,000 4.3 118.5 209 3 D-3 70 2.012,470,000 10.3 119.1 210 4 D-2 40 50.69 561,000 4.1 116.3 211 4 D-3 7070.02 208,000 3.6 111.0 212 4 D-4 130 56.70 304,000 8 107.8 213 7 D-2 400.99 1,766,000 8.5 119.0 214 8 D-2 40 6.58 1,537,000 5.4 115.8 215 8 D-370 3.27 1,569,000 9.1 118.5 216 6 D-2 40 75.52 97,000 15.6 119.0 217 6D-3 70 147.27 49,000 7.1 119.6 218 6 D-4 130 1.26 58,000 8.6 118.2 21912 D-3 70 1.26 1,649,000 8.1 123.2 220 15 D-2 40 1.11 1,975,000 5.9115.0 221 15 D-3 70 0.90 1,174,000 20 116.4 222 10 D-2 40 3.00 696,64814.2 120.9 223 10 D-3 70 3.81 5,000 3 121.7 224 18 D-2 40 1.29 1,363,00010.5 115.8 225 18 D-3 70 1.23 700,000 9.9 117.3 226 22 D-2 40 19.491,132,000 13.3 115.2 227 22 D-3 70 78.06 548,000 11.5 113.2 228 22 D-4130 1.17 564,000 6.3 123.3 229 25 D-2 40 11.39 167,000 4.4 130.3 230 25D-3 70 27.03 138,000 3 124.2 231 27 D-2 40 29.16 520,000 3.9 125.7 23226 D-2 40 27.44 152,000 3.7 126.1 233 26 D-3 70 55.61 108,000 2.8 125.3234 28 D-2 40 107.08 346,000 4.4 123.6 235 28 D-3 70 28.23 232,000 3.8121.3 236 24 D-2 40 5.07 773,000 22.1 124.0 237 24 D-3 70 3.09 969,0003.9 121.7 *×10⁶ g polymer/mol-cat/hr

Example 238

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 40° C. It was the charged with propyleneuntil it was pressurized to 0.20 MPa, and the pressure was stabilized.Thereto a solution of triisobutylaluminum in hexane (40 μL, 1.0 M, KantoKagaku), triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol)and N-[2-(1-indenyl)phenylmethyl]-N-phenylamido titanium dichloride(0.10 gμmol) were added, and polymerization was carried out for 20 min.As a result of polymerization, a polymer having the molecular weight(Mw) of 712,000, the molecular weight distribution (Mw/Mn) of 3.7 and Tmof 127.7° C. was produced in an amount of 4.41×10⁶ g per 1 mol oftitanium and per an hour.

Example 239

An autoclave was charged with toluene (5.0 mL) under nitrogen and thetemperature was stabilized at 40° C. It was then charged with propyleneuntil it was pressurized to 0.20 MPa, and the pressure was stabilized.Thereto a solution of triisobutylaluminum in hexane (40 μL, 1.0 M, KantoKagaku), dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol)and N-[2-(1-indenyl)phenylmethyl]-N-phenylamido titanium dichloride(0.10 μmol) were added, and polymerization was carried out for 20 min.As a result of polymerization, a polymer having the molecular weight(Mw) of 678,000, the molecular weight distribution (Mw/Mn) of 3.8 and Tmof 135.6° C. was produced in an amount of 2.10×10⁶ g per 1 mol oftitanium and per an hour.

INDUSTRIAL APPLICABILITY

According to the present invention, a transition metal complex can beobtained using a ligand intermediate that can be produced and handledmore easily, without using a

-   -   silicon compound that is sensitive to moisture and difficult to        be handled as a key intermediate. Since said transition metal        complex is useful as a catalyst component for production of        various olefin polymers, the present invention especially makes        a significant contribution to    -   the art of production of olefin polymers.

1. A transition metal complex represented by the formula (I):

wherein M represents a Group 4 transition metal; —Y— represents (c):—C(R¹)=A¹- or (d):

wherein A¹ and A² coordinate to M; A represents a Group 16 element, andA¹ and A² each represent a Group 15 element; R¹ and R²⁰ are the same ordifferent and each represents a hydrogen atom, an optionally substitutedC₁₋₁₀ alkyl group, an optionally substituted C₆₋₂₀ aryl group or anoptionally substituted C₇₋₂₀ aralkyl group; R³⁰ represents a hydrogenatom, an optionally substituted C₁₋₁₀ alkyl group, an optionallysubstituted C₆₋₂₀ aryl group, an optionally substituted C₇₋₂₀ aralkylgroup or a silyl group optionally substituted with optionallysubstituted C₁₋₂₀ hydrocarbon group(s); R², R³, R⁴ and R⁵ are the sameor different and each represents a hydrogen atom, an optionallysubstituted C₁₋₁₀ alkyl group, an optionally substituted C₁₋₁₀ alkoxygroup, an optionally substituted C₆₋₂₀ aryl group, an optionallysubstituted C₆₋₂₀ aryloxy group, an optionally substituted C₇₋₂₀ aralkylgroup, an optionally substituted C₇₋₂₀ aralkyloxy group, a silyl groupsubstituted with optionally substituted C₁₋₂₀ hydrocarbon group(s), or aC₁₋₂₀ hydrocarbon-substituted amino group; R⁶, R¹, R⁸ and R⁹ are thesame or different and each represents a hydrogen atom, a halogen atom,an optionally substituted C₁₋₁₀ alkyl group, an optionally substitutedC₁₋₁₀ alkoxy group, an optionally substituted C₆₋₂₀ aryl group, anoptionally substituted C₆₋₂₀ aryloxy group, an optionally substitutedC₇₋₂₀ aralkyl group, an optionally substituted C₇₋₂₀ aralkyloxy group, asilyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), or a C₁₋₂₀ hydrocarbon-substituted amino group; X¹ and X² arethe same or different and each represents a hydrogen atom, a halogenatom, an optionally substituted C₁₋₁₀ alkyl group, an optionallysubstituted C₁₋₁₀ alkoxy group, an optionally substituted C₆₋₂₀ arylgroup, an optionally substituted C₆₋₂₀ aryloxy group, an optionallysubstituted C₇₋₂₀ aralkyl group, an optionally substituted C₇₋₂₀aralkyloxy group or a C₁₋₂₀ hydrocarbon-substituted amino group, or X¹and X², R¹ and R²⁰, the adjacent R², R³, R⁴ and R⁵ or the adjacent R⁶,R⁷, R⁸ and R⁹ may be linked to each other to form a ring, provided thatwhen —Y— represents (a), there is no case that both R¹ and R²⁰ representhydrogen atoms and R², R³, R⁴ and R⁵ are taken together with thecyclopentadiene ring to form a 2-methylinden-1-yl group.
 2. Thetransition metal complex according to claim 1, wherein R¹ and R²⁰ arethe same or different and each represents a hydrogen atom, a C₁₋₁₀ alkylgroup optionally substituted with halogen atom(s), a C₆₋₂₀ aryl groupoptionally substituted with halogen atom(s) or a C₇₋₂₀ aralkyl groupoptionally substituted with halogen atom(s); R³⁰ represents a hydrogenatom, a C₁₋₁₀ alkyl group optionally substituted with halogen atom(s), aC₆₋₂₀ aryl group optionally substituted with halogen atom(s), a C₇₋₂₀aralkyl group optionally substituted with halogen atom(s) or a silylgroup which is optionally substituted with C₁₋₂₀ hydrocarbon(s)optionally substituted with halogen atom(s); R², R³, R⁴ and R⁵ are thesame or different and each represents a hydrogen atom, a C₁₋₁₀ alkylgroup optionally substituted with halogen atom(s), a C₁₋₁₀ alkoxy groupoptionally substituted with halogen atom(s), a C₆₋₂₀ aryl groupoptionally substituted with halogen atom(s), a C₆₋₂₀ aryloxy groupoptionally substituted with halogen atom(s), a C₇₋₂₀ aralkyl groupoptionally substituted with halogen atom(s), a C₇₋₂₀ aralkyloxy groupoptionally substituted with halogen atom(s), a silyl group which issubstituted with C₁₋₂₀ hydrocarbon group(s) optionally substituted withhalogen atom(s) or a C₁₋₂₀ hydrocarbon-substituted amino group; R⁶, R⁷,R⁸ and R⁹ are the same or different and each represents a hydrogen atom,a halogen atom, a C₁₋₁₀ alkyl group optionally substituted with halogenatom(s), a C₁₋₁₀ alkoxy group optionally substituted with halogenatom(s), a C₆₋₂₀ aryl group optionally substituted with halogen atom(s),a C₆₋₂₀ aryloxy group optionally substituted with halogen atom(s), aC₇₋₂₀ aralkyl group optionally substituted with halogen atom(s), a C₇₋₂₀aralkyloxy group optionally substituted with halogen atom(s), a silylgroup which is substituted with C₁₋₂₀ hydrocarbon group(s) optionallysubstituted with halogen atom(s), or a C₁₋₂₀ hydrocarbon-substitutedamino group; X¹ and X² are the same or different and each represents ahydrogen atom, a halogen atom, a C₁₋₁₀ alkyl group optionallysubstituted with halogen atom(s), a C₁₋₁₀ alkoxy group optionallysubstituted with halogen atom(s), a C₆₋₂₀ aryl group optionallysubstituted with halogen atom(s), a C₆₋₂₀ aryloxy group optionallysubstituted with halogen atom(s), a C₇₋₂₀ aralkyl group optionallysubstituted with halogen atom(s), a C₇₋₂₀ aralkyloxy group optionallysubstituted with halogen atom(s), or a C₁₋₂₀ hydrocarbon-substitutedamino group.
 3. The transition metal complex according to claim 1,wherein R¹, R²⁰ and R³⁰ are the same or different and each represents ahydrogen atom, a C₁₋₁₀ alkyl group, a C₆₋₂₀ aryl group or a C₇₋₂₀aralkyl group; R², R³, R⁴ and R⁵ are the same or different and eachrepresents a hydrogen atom, a C₁₋₁₀ alkyl group, a C₁₋₁₀ alkoxy group, aC₆₋₂₀ aryl group, a C₆₋₂₀ aryloxy group, a C₇₋₂₀ aralkyl group, a C₇₋₂₀aralkyloxy group, a silyl group substituted with C₁₋₂₀ hydrocarbongroup(s) or a C₁₋₂₀ hydrocarbon-substituted amino group; R⁶, R⁷, R⁸ andR⁹ are the same or different and each represents a hydrogen atom, ahalogen atom, a C₁₋₁₀ alkyl group, a C₁₋₁₀ alkoxy group, a C₆₋₂₀ arylgroup, a C₆₋₂₀ aryloxy group, a C₇₋₂₀ aralkyl group, a C₇₋₂₀ aralkyloxygroup, a silyl group substituted with C₁₋₂₀ hydrocarbon group(s) or aC₁₋₂₀ hydrocarbon-substituted amino group; X¹ and X² are the same ordifferent and each represents a hydrogen atom, a halogen atom, a C₁₋₁₀alkyl group, a C₁₋₁₀ alkoxy group, a C₆₋₂₀ aryl group, a C₆₋₂₀ aryloxygroup, a C₇₋₂₀ aralkyl group, a C₇₋₂₀ aralkyloxy group or a C₁₋₂₀hydrocarbon-substituted amino group.
 4. The transition metal complexaccording to claim 1 or 2, wherein M represents Ti or Zr. 5-9.(canceled)
 10. The transition metal complex according to claim 1,represented by the formula (I-3), which is the formula (I) wherein —Y—is (d):

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R³⁰, A¹, A², X¹, X² and M havethe same meanings as defined in the formula (I).
 11. The transitionmetal complex according to claim 10, wherein A¹ and A² in the formula(I-3) are each a nitrogen atom.
 12. The transition metal complexaccording to claim 1, represented by the formula (I-4), which is theformula (I) wherein —Y— is (c):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, X¹, X² and M have thesame meanings as defined in the formula (I).
 13. The transition metalcomplex according to claim 12, wherein A in the formula (I-4) is anitrogen atom.
 14. The transition metal complex according to claim 10 or12, wherein R², R³, R⁴ and R⁵ are the same or different and eachrepresents a hydrogen atom or a C₁₋₅ alkyl group.
 15. The transitionmetal complex according to claim 10 or 12, wherein X¹ and X² are thesame or different and each represents a halogen atom, a C₁₋₁₀ alkylgroup, a C₇₋₂₀ aralkyl group, a C₆₋₂₀ aryl group or a C₁₋₂₀hydrocarbon-substituted amino group.
 16. The transition metal complexaccording to claim 15, wherein X¹ and X² are each a halogen atom or aC₁₋₁₀ hydrocarbon-substituted amino group, R², R³, R⁴ and R⁵ are each amethyl group, and R⁶, R⁷, R⁸ and R⁹ are each a hydrogen atom.
 17. Acatalyst for olefin polymerization comprising the transition metalcomplex of any one of claims 1, 10 and 12 in combination with thefollowing compound (A), wherein (A) represents at least one compoundselected from the following compounds (A1) to (A3): (A1): an organicaluminum compound represented by the formula E1_(a)Al(Z)_((3-a)), (A2):cyclic aluminoxane having the structure represented by the formula{—Al(E2)-O—}_(b), (A3): linear aluminoxane having the structurerepresented by the formula E3{-Al(E3)-O—}_(c)Al(E3)₂, wherein E1 to E3are the same or different and each represents a C1-8 hydrocarbon group;Z is the same or different and represents a hydrogen atom or a halogenatom; a is 1, 2 or 3, b is an integer of not less than 2, and c is aninteger of not less than
 1. 18. The catalyst for olefin polymerizationaccording to claim 17, which further comprises (B), wherein (B)represents at least one compound selected from the following compounds(B1) to (B3): (B1): a boron compound represented by the formula BQ₁Q₂Q₃,(B2): a boron compound represented by the formula Z+(BQ₁Q₂Q₃Q₄)⁻, (B3):a boron compound represented by the formula (L-H)⁺(BQ₁Q₂Q₃Q₄)⁻, whereinB is a boron atom in a trivalent valence state; Q1 to Q4 are the same ordifferent and each represents a halogen atom, a C₁₋₂₀ hydrocarbon group,a C₁₋₂₀ halogenated hydrocarbon group, a silyl group substituted withC₁₋₂₀ hydrocarbon group(s), a C₁₋₂₀ alkoxy group or an amino groupsubstituted with two C₂₋₂₀ hydrocarbon groups; L-H represents a Brønstedacid; Z are the same or different and represents a hydrogen atom or ahalogen atom.
 19. A process for producing an olefin polymer, whichcomprises polymerizing olefin using the catalyst for olefinpolymerization according to claim
 17. 20-27. (canceled)
 28. A processfor producing the transition metal complex represented by the formula(I) according to claim 1, wherein X¹ and X² are as defined below, whichcomprises reacting a substituted cyclopentadiene compound represented bythe formula (II)

wherein —Y′ represents (c′): —C(R¹)=A¹-H or

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²⁰, R³⁰, A, A¹ and A² have the samemeanings as defined in claim 1: provided that 1) when —Y′ represents(a′), neither R² and R³ nor R⁴ and R⁵ are linked to each other and takentogether with the cyclopentadiene ring to form a fluorene ring or anindenyl ring, and 2) the compound represented by the formula (II) is not2-(4-methoxyinden-1-yl)benzonitrile, with a transition metal compoundrepresented by the formula (III)MX¹X²X³X⁴  (III) wherein M represents a Group 4 transition metal; X¹,X², X¹ and X⁴ are the same or different and each represents a hydrogenatom, a C₁₋₁₀ alkyl group, a C₁₋₁₀ alkoxy group, a C₆₋₂₀ aryl group, aC₆₋₂₀ aryloxy group, a C₇₋₂₀ aralkyl group, a C₇₋₂₀ aralkyloxy group ora C₁₋₂₀ hydrocarbon-substituted amino group.
 29. The process forproducing the transition metal complex represented by the formula (I)according to claim 28, wherein X¹, X², X³ and X⁴ in the formula (III)each represent a C₁₋₅ hydrocarbon-substituted amino group. 30-35.(canceled)
 36. A carbonyl compound represented by a formula (I):

wherein R¹ represents a hydrogen atom, an optionally substituted C₁₋₁₀alkyl group, an optionally substituted C₆₋₂₀ aryl group or an optionallysubstituted C₇₋₂₀ aralkyl group; R², R³, R⁴ and R⁵ are the same ordifferent and each independently represents a hydrogen atom, anoptionally substituted C₁₋₁₀ alkyl group, an optionally substitutedC₁₋₁₀ alkoxy group, an optionally substituted C₆₋₂₀ aryl group, anoptionally substituted C₆₋₂₀ aryloxy group, an optionally substitutedC₇₋₂₀ aralkyl group, an optionally substituted C₇₋₂₀ aralkyloxy group, asilyl group substituted with optionally substituted C₁₋₂₀ hydrocarbongroup(s), or a C₁₋₂₀ hydrocarbon-substituted amino group; R⁶, R⁷, R⁸ andR⁹ are the same or different and each independently represents ahydrogen atom, a halogen atom, an optionally substituted C₁₋₁₀ alkylgroup, an optionally substituted C₁₋₁₀ alkoxy group, an optionallysubstituted C₆₋₂₀ aryl group, an optionally substituted C₆₋₂₀ aryloxygroup, an optionally substituted C₇₋₂₀ aralkyl group, an optionallysubstituted C₇₋₂₀ aralkyloxy group, a silyl group substituted withoptionally substituted C₁₋₂₀ hydrocarbon group(s) or a C₁₋₂₀hydrocarbon-substituted amino group, or the adjacent R², R³, R⁴ and R⁵and the adjacent R⁶, R⁷, R⁸ and R⁹ are linked to each other to form abenzene ring or a cycloalkylene ring; provided that 1) the positions ofthe double bonds of the cyclopentadiene ring are optional or thecyclopentadiene ring represents a mixture of compounds having doublebonds at any positions, and 2) neither R² and R³ nor R⁴ and R⁵ arelinked to each other and taken together with the cyclopentadiene ring toform a fluorene ring or an indenyl ring.
 37. The carbonyl compoundaccording to claim 36, wherein for R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹in the formula (1), the optionally substituted C₁₋₁₀ alkyl group is aC₁₋₁₀ alkyl group optionally substituted with halogen atom(s), theoptionally substituted C₆₋₂₀ aryl group is a C₆₋₂₀ aryl group optionallysubstituted with halogen atom(s), and the optionally substituted C₇₋₂₀aralkyl group is a C₇₋₂₀ aralkyl group optionally substituted withhalogen atom(s), and for R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹, theoptionally substituted C₁₋₁₀ alkoxy group is a C₁₋₁₀ alkoxy groupoptionally substituted with halogen atom(s), the optionally substitutedC₆₋₂₀ aryloxy group is a C₆₋₂₀ aryloxy group optionally substituted withhalogen atom(s), the optionally substituted C₇₋₂₀ aralkyloxy group is aC₇₋₂₀ aralkyloxy group optionally substituted with halogen atom(s), andthe silyl group substituted with optionally substituted C₁₋₂₀hydrocarbon group(s) is a silyl group which is substituted with C₁₋₂₀hydrocarbon group(s) optionally substituted with halogen atom(s). 38.The carbonyl compound according to claim 36, wherein R¹ represents ahydrogen atom, a C₁₋₁₀ alkyl group, a C₆₋₂₀ aryl group or a C₇₋₂₀aralkyl group; R², R³, R⁴ and R⁵ are the same or different and eachindependently represents a hydrogen atom, a C₁₋₁₀ alkyl group, a C₁₋₁₀alkoxy group, a C₆₋₂₀ aryl group, a C₆₋₂₀ aryloxy group, a C₇₋₂₀ aralkylgroup, a C₇₋₂₀ aralkyloxy group, a silyl group substituted with C₁₋₂₀hydrocarbon group(s) or a C₁₋₂₀ hydrocarbon-substituted amino group; R⁶,R⁷, R⁸ and R⁹ are the same or different and each independentlyrepresents a hydrogen atom, a halogen atom, a C₁₋₁₀ alkyl group, a C₁₋₁₀alkoxy group, a C₆₋₂₀ aryl group, a C₆₋₂₀ aryloxy group, a C₇₋₂₀ aralkylgroup, a C₇₋₂₀ aralkyloxy group, a silyl group substituted with C₁₋₂₀hydrocarbon group(s) or a C₁₋₂₀ hydrocarbon-substituted amino group, orthe adjacent R², R³, R⁴ and R⁵ and the adjacent R⁶, R⁷, R⁸ and R⁹ arelinked to each other to form a benzene ring or a cycloalkylene ring. 39.The carbonyl compound according to claim 36 or 37, wherein R², R³, R⁴and R⁵ are the same or different and each independently represents ahydrogen atom or a C₁₋₅ alkyl group.
 40. The carbonyl compound accordingto any one of claims 36 to-38, wherein R¹ is a hydrogen atom, a C₁₋₅alkyl group or a C₆₋₁₀ aryl group. 41-44. (canceled)
 45. A process forproducing an olefin polymer, which comprises polymerizing olefin usingthe catalyst for olefin polymerization according to claim
 18. 46. Thecarbonyl compound according to claim 39, wherein R¹ is a hydrogen atom,a C₁₋₅ alkyl group or a C₆₋₁₀ aryl group.
 47. A process for producingthe transition metal complex represented by the formula (1) according toclaim 1 wherein at least one of X¹ and X² is halogen, which comprisesreacting a transition metal complex represented by the formula (I)according to claim 1 wherein at least one of X¹ and X² is a C₁₋₂₀hydrocarbon-substituted amino group, with a halogen compound selectedfrom a chlorosilane compound and hydrogen chloride.